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RECENT PROGRESS IN
ORBITAL-FREE DENSITY
FUNCTIONAL THEORY
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Recent Advances in Computational Chemistry
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Editor-in-Charge
Delano P. Chong, Department of Chemistry, University of British Columbia,
Canada

Published
Recent Advances in Density Functional Methods, Part I (Volume 1)
ed. D. P. Chong
Recent Advances in Density Functional Methods, Part II (Volume 1)
ed. D. P. Chong
Recent Advances in Density Functional Methods, Part III (Volume 1)
eds. V. Barone, A. Bencini and P. Fantucci
Recent Advances in Quantum Monte Carlo Methods, Part I (Volume 2)
ed. W. A. Lester
Recent Advances in Coupled-Cluster Methods (Volume 3)
ed. Rodney J. Bartlett
Recent Advances in Multireference Methods (Volume 4)
ed. K. Hirao
Recent Advances in Relativistic Molecular Theory (Volume 5)
eds. K. Hirao and Y. Ishikawa

Forthcoming
Recent Advances in Computational Chemistry Software (Volume 7)
eds. R. Amos and R. Kobayashi
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RECENT PROGRESS IN
ORBITAL-FREE DENSITY
FUNCTIONAL THEORY

edited by

Tomasz A Wesolowski
University of Geneva, Switzerland

Yan Alexander Wang


University of British Columbia, Canada
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Recent progress in orbital-free density functional theory / edited by Tomasz A Wesolowski,
University of Geneva, Switzerland, Yan Alexander Wang, University of British Columbia,
Canada.
pages cm. -- (Recent advances in computational chemistry ; volume 6)
Includes bibliographical references and index.
ISBN 978-9814436724 (hardcover : alk. paper)
1. Density functionals. 2. Chemistry--Mathematics. 3. Atomic orbitals.
I. Wesolowski, Tomasz A. II. Wang, Yan Alexander.
QD462.6.D45R45 2013
541'.28--dc23

2012046733

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Preface

The interest in orbital-free density-functional-theory based methods (OF-DFT )


originates from the fact that they are built upon a sound theory, which, in principle,
makes it possible to describe the ground state of a multi-electron system exactly
without constructing the wave function explicitly. This feature opens the door for
practical modeling very large and complex polyatomic systems of millions of atoms
accurately. The computational cost of OF-DFT calculations grows quasi-linearly
with the size of the system, allowing one to break the barrier of the highly nonlin-
ear growth in the computational costs of conventional wave-function based meth-
ods. Converting this virtually exact theory into an effective computational method
proved, however, to be a formidable task in practice. The first attempts were made
in the late 1920’s independently by Thomas and Fermi, shortly after the birth of
quantum theory. Unfortunately, such early Thomas-Fermi models, hampered by
poor accuracy, offered no potential usefulness for studies of chemical problems. The
chemistry community seemed to have lost interest in OF-DFT following the demon-
stration by Teller that molecules described using the original Thomas-Fermi model
always dissociate. The use of orbitals appeared indispensable. Approximating the
exact quantities by density functionals could be accepted only for the smaller com-
ponents of the total energy as it was made in the celebrated Xα method of Slater,
which showcased the appeal of electron-density based methods and which led ulti-
mately to the modern density functional theory (DFT) formulated by Hohenberg
and Kohn in the middle of 1960’s. To bypass the poor density-only approximation
to the kinetic energy, Kohn and Sham devised an orbital-based formal framework
for numerical simulations, which is commonly known as the Kohn-Sham method
nowadays. The Kohn-Sham DFT is based on density-only OF-DFT of Hohenberg
and Kohn but the orbitals are used nevertheless as auxiliary quantities in order to
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avoid explicit density-only approximations for the kinetic energy.


Although the efforts to bring life back to OF-DFT never ceased ever since, the
progress was rather slow. The advance in the OF-DFT methods was hindered by
the difficulty in constructing sufficiently accurate approximations to the electron-
density functional for the kinetic energy of a many-electron system. Not until
the 1990’s, many research groups, mainly driven by the ever-increasing appetite
for modeling bigger complex systems in many fields, began to work intensively to
revitalize OF-DFT methods. Over the last two decades, OF-DFT methods have

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vi Preface
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achieved a certain level of maturity and can be considered as the optimal tool
for simulating certain static and dynamic phenomena in soft- and hard condensed
matter.
To facilitate the research progress, a series of symposia exclusively dedicated to
exhibit the latest developments of OF-DFT methods have been in operation since
the early 2000’s. The earliest OF-DFT symposium was the CECAM workshop on
“Approximating and Applying of the Kinetic Energy Functional ” organized by T.A.
Wesolowski and H. Chermette at Lyon, France, on 31 July–2 August 2002. The
second OF-DFT symposium, “Explicit Density Functional of the Kinetic Energy in
Computer Simulations at Atomistic Level,” was organized by T.A. Wesolowski at the
International Conference of Computational Methods in Sciences and Engineering,
in Loutraki, Korinthos, Greece, on 23–24 October 2005. The third OF-DFT sympo-
sium, “Orbital-Free Density Functional Theory,” was organized by T.A. Wesolowski
and Y.A. Wang at the Sixth Congress of the International Society for Theoretical
Chemical Physics, in Vancouver, Canada, on 23–24 July 2008.
At this critical junction, during a conversation over a dinner at the second OF-
DFT symposium, we came up an idea to collect in a single volume the accounts of
representative developments in various interconnected sub-domains related to the
kinetic energy density functional and its applications. Thus, the common denom-
inator of all chapters in the present volume is the kinetic energy functional - the
quest for a better approximation to this functional unifies the contributors from
many different fields.
The first part of the present volume starts with contributions focusing on ex-
act properties of the kinetic energy density functional (Chapters 1-3). Chapters
4-8, focus rather on practical applications of OF-DFT in numerical simulations.
They provide a representative overview of those key developments leading to the
current stage of the OF-DFT methods. The reported numerical simulations supply
convincing evidence that the constantly expanding domain of applicability of the
OF-DFT methods now includes solids, large clusters, and liquids.
The second part of this volume deals with formalisms and methods, which are
closely related to OF-DFT, but hinge on approximations to the bi-functional for the
non-additive kinetic energy: subsystem DFT and Frozen-Density Embedding Theory
(FDET ). In subsystem DFT, which was proposed originally in papers by Senatore
and Subbaswamy and by Cortona for simulating solids, introduced latter for molec-
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ular interactions by Wesolowski and collaborators, sets of Kohn-Sham-like orbitals


for each subsystem are used as auxiliary quantities. The non-interacting reference
wave function for the whole system as in the Kohn-Sham case is not constructed.
As a consequence, evaluation of the total kinetic energy requires approximating the
non-additive kinetic energy. FDET on the other hand was introduced originally by
Wesolowski and Warshel as the formal basis for multi-level simulations. In FDET,
the orbital level of description applies only for selected part of the total system.
Although FDET is also based on Hohenberg-Kohn theorems, it does not target the

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Preface vii
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ground-state energy of a given system as do the OF-DFT, Kohn-Sham DFT, and


subsystem DFT methods, but aims rather at the upper bound of this energy. In
Chapter 9, an analytically solvable model system is used to introduce the basic ele-
ments of FDET and to overview the challenges in approximating the non-additive
kinetic potential. Chapters 10-11 review the recent developments and applications
of computational methods which apply approximations for the non-additive kinetic
energy. Chapter 12, on the other hand focuses on qualitative differences between
quantities defined in subsystem DFT and their counterparts obtained if approxima-
tions for the non-additive kinetic energy are used.
The third part of this volume covers mainly the use of the kinetic energy and
related quantities in interpreting key chemical concepts. Chapters 13-15 deliver a
comprehensive overview of the relations between the kinetic energy density func-
tional and the Fisher information.
In the Appendix, the analytical expressions used in the literature to approx-
imate the kinetic energy and related quantities are collected together with a full
bibliography.
Finally, we have to stress that the contributors to that volume come from dif-
ferent fields and despite the common interest in the kinetic energy functional, the
used terminology and conventions are not uniform. We only partially addressed
this issue of by pointing out equivalent terms or by identifying similar terms used
for various quantities in Subject Index or in the Editors’ Note.
We hope that this very first volume devoted to OF-DFT will enable scientific
community to gain a deeper appreciation of the state of the art of OF-DFT methods.
Consequently, more people will be attracted to work in this promising research field
to propel OF-DFT methods into the world of main-stream ab initio simulations.
Tomasz Adam Wesolowski & Yan Alexander Wang
June 2012
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Contents

Preface v

Part 1: Density Functional for the Kinetic Energy and


Its Applications in Orbital-Free DFT Simulations 1

1. From the Hohenberg-Kohn Theory to the Kohn-Sham Equations 3


Y. A. Wang & P. Xiang

2. Accurate Computation of the Non-Interacting Kinetic Energy


from Electron Densities 13
F. A. Bulat & W. Yang

3. The Single-Particle Kinetic Energy of Many-Fermion Systems:


Transcending the Thomas-Fermi plus Von Weizsäcker Method 31
G. G. N. Angilella & N. H. March

4. An Orbital Free ab initio Method: Applications to Liquid Metals


and Clusters 55
A. Aguado, D. J. González, L. E. González, J. M. López,
S. Núñez & M. J. Stott
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5. Electronic Structure Calculations at Macroscopic Scales using


Orbital-Free DFT 147
B. G. Radhakrishnan & V. Gavini

6. Properties of Hot and Dense Matter by Orbital-Free Molecular


Dynamics 165
F. Lambert, J. Clérouin, J.-F. Danel, L. Kazandjian & S. Mazevet

ix

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x Contents
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7. Shell-Correction and Orbital-Free Density-Functional Methods


for Finite Systems 203
C. Yannouleas & U. Landman

8. Finite Element Approximations in Orbital-Free Density


Functional Theory 251
H. Chen & A. Zhou

Part 2: The Functional for the Non-Additive Kinetic Energy


and Its Applications in Numerical Simulations 273

9. Non-Additive Kinetic Energy and Potential in Analytically


Solvable Systems and Their Approximated Counterparts 275
T. A. Wesolowski & A. Savin

10. Towards the Description of Covalent Bonds in Subsystem Density-


Functional Theory 297
Ch. R. Jacob & L. Visscher

11. Orbital-Free Embedding Calculations of Electronic Spectra 323


J. Neugebauer

12. On the Principal Difference Between the Exact and Approximate


Frozen-Density Embedding Theory 355
O. V. Gritsenko

Part 3: Kinetic Energy Functional and Information Theory 367

13. Analytic Approach and Monte Carlo Sampling for Electron Correlations 369
L. M. Ghiringhelli & L. Delle Site
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14. Kinetic Energy and Fisher Information 387


Á. Nagy

15. Quantum Fluctuations, Dequantization, Information Theory and


Kinetic-Energy Functionals 401
I. P. Hamilton, R. A. Mosna & L. Delle Site

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Contents xi
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Part 4: Appendix 427

16. Semilocal Approximations for the Kinetic Energy 429


F. Tran & T. A. Wesolowski

Author Index 443

Subject Index 445


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PART 1

Density Functional for the Kinetic Energy


and Its Applications in Orbital-Free DFT
Simulations
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Chapter 1

From the Hohenberg-Kohn Theory to the Kohn-Sham Equations

Yan Alexander Wang* and Ping Xiang


Department of Chemistry, University of British Columbia
Vancouver, British Columbia, Canada V6T 1Z1
yawang@chem.ubc.ca

Two existing ways of deriving the Kohn-Sham equations were analyzed in great
details. It turns out that both are incomplete in principle because they will
lead to a paradox. It was further shown that the paradox can be resolved by
introducing some arbitrary constants in the total Kohn-Sham effective poten-
tial. As a result, the functional derivative of the kinetic-energy density func-
tional of the auxiliary non-interacting system within the Kohn-Sham method
can be exactly calculated only from the highest occupied Kohn-Sham orbital
2 KS
φKS KS KS
H (r): δTs [ρ]/δρ0 (r) = −0.5{∇ φH (r)}/φH (r) = −I − {veff (r)}can , where I
KS
and {veff (r)}can are the first (lowest) ionization energy and the canonical repre-
sentative of the total Kohn-Sham effective potential, respectively.

Contents
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 Routes to the Kohn-Sham equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 A paradox and its resolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 The Wang paradox . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.2 The Wang-Parr resolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.4 Direct inclusion of the constraints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.5 Functional derivative of the kinetic-energy density functional . . . . . . . . . . . . . . 10
1.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
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1.1. Introduction

Two papers published over 45 years ago by Hohenberg, Kohn, and Sham (HKS)1,2
laid the foundation for modern density-functional theory.3–14 The two Hohenberg-
Kohn (HK) theorems1 first legitimatized the ground-state (GS) electron density
ρ0 (r) as the basic variable of the GS quantum chemistry and the Kohn-Sham (KS)
method2 then offered a specific numerical implementation for this theory. Later,
the HKS theory was recasted in the constrained-search formulation.3–5,15–20
The first HK theorem1 guarantees that, for an N -electron quantum chemical

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4 Y. A. Wang & P. Xiang


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system, its total GS electronic energy is a functional of ρ0 (r):

E[Ψ0 ] ≡ E[ρ0 ] , (1.1)

where Ψ0 is the GS wave function. The second HK theorem1 insures that, for a
fixed external potential v(r), any trial density ρ(r) coming from N -electron wave
functions in Hilbert space (HS) corresponds to a higher energy than the GS energy:

Ev [ρ] > Ev [ρ0 ] . (1.2)

If Ev [ρ] is differentiable in the vicinity of ρ0 (r),3–9,12–14 this variational principle


can be reexpressed as9,14
 
δEv
dEv [ρ0 ] = δρ(r) = 0 , (1.3)
δρ0 (r)
with the normalization condition,

hδρ(r)i ≡ 0 . (1.4)

According to a theorem by Gelfand and Fomin,21,22 one immediately has


δEv
= µHS , (1.5)
δρ0 (r)

where µHS is a constant,9,12–14,23–25 and the subscript “HS” denotes the N -electron
HS as the variational domain. If the functional form of Ev [ρ] is explicitly given, µHS
will be a fixed number for a specific ρ0 (r); otherwise, it is normally believed that µHS
can only be determined up to an arbitrary constant in HS.9 However, theoretical
considerations in Fock space13,14,23,24 have definitely concluded that

µHS = −I, (1.6)

where I is the first (lowest) ionization energy of the N -electron system.


Because the exact form of Ev [ρ] is unknown for general many-electron systems,
one has to rely on the KS scheme2 to implement the HK theory.1 In the KS
method,2 the basic working equation (in canonical form) is
 KS

t̂ + veff (r) φKS KS KS
i (r) = εi φi (r) , (1.7)
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where the kinetic-energy operator is


1
t̂ ≡ − ∇2 , (1.8)
2
and the total KS effective potential veff
KS
(r) is defined as the functional derivative at
the KS density ρ (r):
KS

KS
δ(Ev [ρKS ] − Ts [ρKS ]) δVs [ρKS ]
veff (r) = = . (1.9)
δρKS (r) δρKS (r)

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From the Hohenberg-Kohn Theory to the Kohn-Sham Equations 5


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Here, Ts [ρKS ] is the non-interacting kinetic-energy density functional, and Vs [ρKS ]


is the difference between Ev [ρKS ] and Ts [ρKS ]. At the solution point, ρKS (r) and
Ts [ρKS ] are recovered from the first N (normalized) KS orbitals {φKS
i (r)}:

N
X 2
ρKS (r) = |φKS
i (r)| , (1.10)
i=1

hρKS (r)i ≡ N, (1.11)

and
N
X
Ts [ρKS ] = hφKS KS
i (r)| t̂ |φi (r)i . (1.12)
i=1

It was claimed that ρKS (r) would be identical to ρ0 (r) at the final solution point.2,9
In the constrained-search formulation,3–5,15–20 Levy and Lieb (LL) propose to
minimize the model kinetic energy,3–5,15–18

N
X
LL LL
Tm [ρ0 ] = min φi (r) t̂ φi (r) , (1.13)
ρ0
i=1

with the exact orbital realization of ρ0 (r),

N
X 2
ρ0 (r) = |φLL
i (r)| . (1.14)
i=1

Then, the effective potential veff


LL
(r) is the local Lagrange-Euler multiplier for Eq.
(1.14), and the first N LL orbitals {φLL
i (r)} satisfy similar working equations to Eq.
(1.7),9
 LL

t̂ + veff (r) φLL LL LL
i (r) = εi φi (r) . (1.15)

A question naturally arises here: Is the KS scheme fully equivalent to the LL


U.S. or applicable copyright law.

proposal? To answer this question, it is necessary to review the details of the


derivations of the KS equations. The existing literature2,9 implies two plausible
routes to the KS equations from the HK theorems.1 The first one was illustrated in
the original KS paper,2 whereas the second one was implied in a book by Parr and
Yang (PY).9 However, it should be noted that neither of the two sources provided
complete details of the derivations.
For simplicity of the notational system, all orbitals will be chosen to be real
and the superscripts on ρKS (r) and φKS
i (r) will be dropped unless otherwise noted
hereafter.

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1.2. Routes to the Kohn-Sham equations

After introducing Eqs. (1.5), (1.10), and (1.12), Kohn and Sham partitioned Ev [ρ]
into two main pieces:2

Ev [ρ] ≡ Ts [ρ] + Vs [ρ] , (1.16)

and hence, one has


δEv [ρ] δTs [ρ] δVs [ρ]
≡ + = µHS , (1.17)
δρ(r) δρ(r) δρ(r)

dEv [ρ] ≡ dTs [ρ] + dVs [ρ] , (1.18)

and
     
δEv [ρ] δTs [ρ] δVs [ρ]
dEv [ρ] ≡ δρ(r) ≡ δρ(r) + δρ(r) . (1.19)
δρ(r) δρ(r) δρ(r)
From Eqs. (1.10) and (1.12), one observes
N
X
δρ(r) = 2 φi (r)δφi (r) , (1.20)
i=1

and
N
X

dTs [{φi }] = 2 δφi (r) t̂ φi (r) . (1.21)
i=1

On setting

dTs [ρ] ≡ dTs [{φi }] , (1.22)

one obtains from Eqs. (1.9) and (1.18)−(1.21) that

dEv [ρ] = dTs [{φi }] + dVs [ρ]


 
δVs [ρ]
= dTs [{φi }] + δρ
δρ
N
X

=2 δφi (r) t̂ φi (r) + hveff
KS
(r) δρ(r)i
U.S. or applicable copyright law.

i=1
N
X N
X


=2 δφi (r) t̂ φi (r) + 2 KS
hδφi (r)|veff (r)|φi (r)i
i=1 i=1
N
X

=2 δφi (r) t̂ + veff
KS
(r) φi (r) . (1.23)
i=1

For arbitrary infinitesimal variations of {δφi }, a minimization of the above equation


with the orthonormality constraint between {φi } arrives at the KS equations.2

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Somewhat differently, Parr and Yang9 wrote the total energy purely in an
orbital-functional form:
Ev [{φi }] ≡ Ts [{φi }] + Vs [{φi }] , (1.24)
and then, one gets
dEv [{φi }] ≡ dTs [{φi }] + dVs [{φi }] . (1.25)
As it is usually done in the literature,25–30 one would believe that
XN  
δVs [{φi }]
dVs [{φi }] = δφi (r) . (1.26)
i=1
δφi (r)
From Eq. (1.10) and the chain rule, one has
δρ(r0 ) ∂ρ(r)
= δ(r0 − r) = 2φi (r)δ(r0 − r) , (1.27)
δφi (r) ∂φi (r)
and
Z
δVs [{φi }] δVs δρ(r0 ) 0 δVs KS
= dr = 2φi (r) = 2veff (r)φi (r) . (1.28)
δφi (r) δρ(r0 ) δφi (r) δρ(r)
Then, with the aid from Eqs. (1.12), (1.25), (1.26), and (1.28), one recovers the KS
equations once again.

1.3. A paradox and its resolution

The pivotal step of the KS derivation is Eq. (1.22), while the crucial procedure
of the PY derivation is the orbital-functional derivatives in Eqs. (1.26)−(1.28).
However, the following arguments seem to refute them both.

1.3.1. The Wang paradox


First, given Eqs. (1.26)−(1.28) were correct, one could do the same trick to Ts [ρ],
such that
δTs δTs [ρ] ∂ρ(r) δTs [ρ]
= = 2φi (r) . (1.29)
δφi (r) δρ(r) ∂φi (r) δρ(r)
From Eq. (1.21), one could obtain
U.S. or applicable copyright law.

δTs
= 2 t̂φi (r) . (1.30)
δφi (r)
From Eqs. (1.7), (1.29), and (1.30), one would readily derive
δTs [ρ] t̂φi (r)
= = εKS KS
i − veff (r) . (1.31)
δρ(r) φi (r)
There is another way to derive Eq. (1.31) through
 
δTs
dTs [ρ] = δρ(r) . (1.32)
δρ(r)

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By substituting Eq. (1.20) into the above equation, one would get
N  
X δTs
dTs [ρ] = 2
δφi (r) φi (r) . (1.33)
i=1
δρ(r)

Applying Eq. (1.22), one would obtain Eq. (1.31) again after comparing Eq. (1.21)
with Eq. (1.33).
However, Eq. (1.31) is obviously incorrect, because the orbital dependence of
the right-hand side is directly contradictory to the property of the left-hand side.
Because the first N KS orbitals are linearly dependent31 via Eqs. (1.10) and (1.11),
Eqs. (1.26)−(1.28) are in error. This point is elucidated more clearly and generally
in the following theorem.32

Theorem 1.1 (Wang-Davidson, 1996). If orthonormal orbitals {ξi (r)} are so-
lutions of a set of coupled variational equations,
 
ĥ0 + ĥ1 [θ] ξi (r) = ωi ξi (r) , (1.34)

with the inter-orbital relations,



X ∞
X
θ(r) = ni ξi2 (r) , and η = ni , (1.35)
i=1 i=1

then, the functional derivative relations,


δξi δni
= δik , and = δik , (1.36)
δξk δnk
are not true in general. Here, the operators on the left-hand side of Eq. (1.34)
consist of a θ-independent ĥ0 and a θ-dependent ĥ1 [θ] (a θ functional), {ωi } are the
eigenvalues of {ξi }, {ni } are the (non-negative) occupation numbers of {ξi }, and η
is a fixed positive number.

Proof. Since Eq. (1.34) is variational, it must hold true after any arbitrary
infinitesimal derivation in {ξi } and {ni },
 
ĥ0 + ĥ1 [θ̃] ξ̃i = ω̃i ξ̃i , (1.37)
U.S. or applicable copyright law.

where {ξ˜i } and θ̃ are the new orbitals and density such that

X 
δξi = ξ̃i − ξi , δni = ñi − ni , and δθ = θ̃ − θ = 2ni ξi δξi + ξi2 δni . (1.38)
i=1

Expanding Eq. (1.37) around the original quantities to first order and deleting
redundant terms, we have
   
ĥ0 + ĥ1 − ωi δξi = δωi − δ ĥ1 ξi , (1.39)

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where
δ ĥ1 = ĥ1 [θ̃] − ĥ1 [θ] = ĥ1 [θ + δθ] − ĥ1 [θ] . (1.40)
33
A simple utilization of first-order perturbation theory yields
X∞
hξk |δ ĥ1 |ξi i
δξi = ξk . (1.41)
ωi − ωk
k6=i

Because of Eqs. (1.38) and (1.40), one concludes that δξi is related to all other
orbital derivations {δξi } through δ ĥ1 in Eq. (1.41). Moreover, because of the fixed
value of η, one knows that
X∞
0 ≡ δη = δni . (1.42)
i=1

Therefore, Eq. (1.36) is untrue in general. 


Because Eq. (1.36) is implicitly employed in Eqs. (1.26)−(1.28), the PY deriva-
tion is invalid.

1.3.2. The Wang-Parr resolution


The error in the Paradox lies in Eq. (1.30) after the false identification of δTs /δφi
from Eq. (1.21). The orthonormality of {φi } simply implies that
hφi |φi i = hφi + δφi |φi + δφi i = 1 , (1.43)
and hence, to first order,
hδφi |φi i = 0 . (1.44)
Then, Eq. (1.21) will be invariant to any amount of addition of Eq. (1.44),
N
X

δTs [{φi }] = 2 δφi t̂ + ci φi , (1.45)
i=1

where {ci } are some arbitrary constants.34 Going through the arguments presented
in the Paradox again, one instead has
δTs 
= 2 t̂ + ci φi (r) , (1.46)
δφi (r)
U.S. or applicable copyright law.

and
δTs [ρ] t̂φi (r)
= + ci = εKS KS
i + ci − veff (r) . (1.47)
δρ(r) φi (r)
With the aid from Eqs. (1.9) and (1.17), one can unambiguously define {ci } as
ci = µHS − εKS
i , (1.48)
such that both sides of Eq. (1.47) are orbital independent. As a result, the Paradox
is avoided. However, it does point out that {ci } have been implicitly absorbed into
the orbital energies {εKS
i } in the KS and PY derivations.

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1.4. Direct inclusion of the constraints

Explicitly enforcing the constraints of Eqs. (1.10) and (1.11) in the KS and PY
derivations only introduces a new local Lagrange-Euler multiplier γ(r) into the KS
effective potential,
KS KS
ṽeff (r) = veff (r) + γ(r) . (1.49)

Then, Eqs. (1.31) and (1.47) become


δTs [ρ]
= (ε̃KS KS
i + c̃i ) − ṽeff (r) , ∀ i . (1.50)
δρ(r)
Multiplying both sides of Eq. (1.50) by δρ(r) and integrating over the entire space,
one obtains
 
δTs [ρ]
dTs = δρ(r) = (ε̃KS KS
i + c̃i ) hδρ(r)i − hveff (r) δρ(r)i − hγ(r) δρ(r)i . (1.51)
δρ(r)
Because of Eqs. (1.4), (1.9), and (1.19), one has

dEv = − hγ(r) δρ(r)i . (1.52)

At the solution point, dEv will be zero for any arbitrary infinitesimal derivation
δρ(r), and hence, γ(r) has to be a constant.21,22 This means that Eq. (1.10) will
be automatically satisfied at the solution point within the KS scheme.
This conclusion together with the discussion presented in the previous section
finalize the full equivalence between all the existing derivations of the KS equations,
besides a possible arbitrary real constant in the effective potentials:
LL KS
veff (r) − veff (r) = constant . (1.53)

In other words, these two effective potentials belong to the same class of local
potentials, [veff (r)], with difference up to a real constant:13

[veff (r)] = {u(r)|u(r) = veff (r) + c, c ∈ R}. (1.54)

Eqs. (1.53) and (1.54) simply restate that the canonical representatives these two
effective potentials are identical:
U.S. or applicable copyright law.

LL KS
{veff (r)}can ≡ {veff (r)}can = veff (r) − veff (∞) ∈ [veff (r)] , (1.55)

where any additive constants of the effective potentials at infinity have been re-
moved.13

1.5. Functional derivative of the kinetic-energy density functional

To this end, we are ready to discuss the exact definition of the functional derivative
of the non-interacting kinetic-energy density functional, δTs [ρ]/δρ0 (r).

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After adopting the canonical representative for the total KS effective potential,
we can employ Eqs. (1.6) and (1.48) to update Eqs. (1.47) and (1.50) to
δTs [ρ] t̂φKS
i (r)
= KS − (I + ε̄KS KS
i ) = −I − {veff (r)}can , (1.56)
δρ0 (r) φi (r)
which simply states that
t̂φKS
i (r)
= ε̄KS KS
i − {veff (r)}can . (1.57)
φi (r)
KS

Here, {ε̄KS
i } are the renormalized KS orbital energies corresponding to {veff (r)}can .
KS

Because {veff
KS
(r)}can is zero at infinity, the renormalized energy of the highest oc-
cupied KS orbital φKS H
(r) is identical to −I,9,13,14,23,24
ε̄KS
H = −I , (1.58)
and consequently δTs [ρ]/δρ0 (r) can be calculated solely from φKS
H
(r):
δTs [ρ] H (r)
t̂φKS KS
= KS = −I − {veff (r)}can , (1.59)
δρ0 (r) φH (r)
which should be used to benchmark all existing approximations and to help de-
sign better approximations to the non-interacting kinetic-energy density func-
tional.11,13,14

1.6. Conclusions

None of the two derivations2,9 of the KS equations is completely correct. However,


both derivations are mutually equivalent up to an arbitrary constant in the KS
effective potential. The functional derivative of the non-interacting kinetic-energy
density functional can be exactly calculated from the highest occupied KS orbital
alone.

Acknowledgement

Financial support for this project was provided by a grant from the Natural Sciences
and Engineering Research Council (NSERC) of Canada. Y.A.W. is grateful for
discussions with Profs. Ernest R. Davidson and Robert G. Parr. Y.A.W. wrote
U.S. or applicable copyright law.

most of the chapter whereas P.X. mainly contributed to the first half of Section 1.4.

References

1. P. Hohenberg and W. Kohn, Phys. Rev. 136, B864 (1964).


2. W. Kohn and L. J. Sham, Phys. Rev. 140, A1133 (1965).
3. E. H. Lieb, in Physics as Nature Philosophy: Essays in Honor of Laszlo Tisza on
His 75th Birthday, edited by H. Feshbach and A. Shimony (MIT Press, Cambridge,
Massachusetts, 1982), p. 111.

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4. E. H. Lieb, Int. J. Quantum Chem. 24, 243 (1983).


5. E. H. Lieb, in Density Functional Methods in Physics, edited by R. M. Dreizler and
J. da Providência (Plenum, New York, 1985), p 31.
6. H. Englisch and R. Englisch, Phys. Status Solidi B 123, 711 (1983).
7. H. Englisch and R. Englisch, Phys. Status Solidi B 124, 373 (1984).
8. H. Englisch and R. Englisch, Physica A 121, 253 (1983).
9. R. G. Parr and W. Yang, Density-Functional Theory of Atoms and Molecules (Oxford
University Press, New York, 1989).
10. R. M. Dreizler and E. K. U. Gross, Density Functional Theory: An Approach to the
Quantum Many-Body Problem (Springer, Berlin, 1990).
11. Y. A. Wang and E. A. Carter, in Theoretical Methods in Condensed Phase Chemistry,
edited by S. D. Schwartz (Kluwer, Dordrecht, 2000), Chap. 5, p. 117.
12. R. van Leeuwen, Adv. Quantum Chem. 43, 25 (2003).
13. F. E. Zahariev and Y. A. Wang, Phys. Rev. A 70, 042503 (2004).
14. Y. A. Zhang and Y. A. Wang, Int. J. Quantum Chem. 109, 3199 (2009).
15. M. Levy, Proc. Natl. Acad. Sci. U.S.A. 76, 6062 (1979).
16. M. Levy, Phys. Rev. A 26, 1200 (1982).
17. M. Levy and J. P. Perdew, in Density Functional Methods in Physics, edited by R.
M. Dreizler and J. da Providência (Plenum, New York, 1985), p. 11.
18. J. K. Percus, Int. J. Quantum Chem. 13, 89 (1978).
19. Y. A. Wang, Phys. Rev. A 55, 4589 (1997).
20. Y. A. Wang, Phys. Rev. A 56, 1646 (1997).
21. I. M. Gelfand and S. V. Fomin, Calculus of Variations (Prentice-Hall, Englewood
Cliffs, NJ, 1963).
22. R. G. Parr and L. J. Bartolotti, J. Phys. Chem. 87, 2810 (1983).
23. Z.-Z. Yang, Y. A. Wang, and S.-B. Liu, Sci. China, Ser. B Chem. 41, 1741 (1998).
24. Z.-Z. Yang, S. Liu, and Y. A. Wang, Chem. Phys. Lett. 258, 30 (1996).
25. R. G. Parr, R. A. Donnelly, M. Levy, and W. E. Palke, J. Chem. Phys. 68, 3801
(1978).
26. R. A. Donnelly and R. G. Parr, J. Chem. Phys. 69, 4431 (1978).
27. R. A. Donnelly, J. Chem. Phys. 71, 2874 (1979).
28. J. D. Talman and W. F. Shadwick, Phys. Rev. A 14, 36 (1976).
29. M. R. Norman and D. D. Koelling, Phys. Rev. B 30, 5530 (1984).
30. J. B. Krieger, Y. Li, and G. J. Iafrata, in Density Functional Theory, edited by E. K.
U. Gross and R. M. Dreizler (Plenum, New York, 1995), p. 191.
31. For a similar discussion about the linear dependence problem, see E. R. Davidson,
Chem. Phys. Lett. 246, 209 (1995).
32. Y. A. Wang and E. R. Davidson, personal communications (1995-1996).
33. For example, A. Szabo and N. S. Ostlund, Modern Quantum Chemistry (Dover, Mi-
neola, New York, 1996).
U.S. or applicable copyright law.

34. Y. A. Wang and R. G. Parr, private discussions (1995-1996).

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Chapter 2

Accurate Computation of the Non-Interacting Kinetic Energy


from Electron Densities

Felipe A. Bulat1,∗ and Weitao Yang2


1
Acoustics Division, Naval Research Laboratory
Washington DC, WA 20375, USA
felipe.bulat-jara.ctr.ci@nrl.navy.mil
2
Department of Chemistry, Duke University
Durham, NC 27708, USA
weitao.yang@duke.edu

We describe a robust and practical method for the computation of implicit den-
sity functionals from electron densities based on a regularized version of the
Wu-Yang method. For any given electron density that is non-interacting v-
representable, our method provides a stable variational solution for calculating
the non-interacting one-electron potential and the non-interacting kinetic energy.
It is thus a computational approach to the challenge of constructing kinetic energy
functionals. We also emphasize its application in the computation of the separate
exchange and correlation components of the exchange-correlation potential.

Contents
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.1 Direct optimization method for the Kohn-Sham kinetic energy functional Ts and
the exact exchange-correlation potential vxc . . . . . . . . . . . . . . . . . . . . 15
2.2.2 Exchange vx and correlation vc components of the exchange-correlation potential
vxc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3 Regularization of the WY functional . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.4 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.4.1 Exchange-correlation vxc (r) potentials . . . . . . . . . . . . . . . . . . . . . . . 21
U.S. or applicable copyright law.

2.4.2 Kohn-Sham kinetic energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22


2.4.3 Exchange vx (r) and correlation vc (r) potentials . . . . . . . . . . . . . . . . . . 24
2.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

2.1. Introduction

Density Functional Theory (DFT)1–5 is, perhaps, the most widely used electronic
∗ Under contract from Global Strategies Group (North America) Inc., Crofton, MD 21114, USA.

13

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structure method. To a large extent the success of DFT is due to the cost-effective
consideration of electron correlation effects within the Kohn-Sham framework.2 Al-
thought increasingly accurate exchange-correlation density functional approxima-
tions (DFA) have been developed over the years,6–19 there remains a multitude of
challenges20 and limitations that future DFAs should aim to overcome. Most of
these limitations can be related to the fact that approximate exchange-correlation
functionals are not explicitly discontinuous,21 and thus markedly deviate from the
exact behaviour for fractional charges and fractional spins.21,22 While the energy
of a system with N + δ electrons (0 < δ < 1) should be a linear combination of the
energy of the N -and N + 1-electron systems ((1 − δ)E[N ] + δE[N + 1]), all current
DFAs violate this condition to various extents (delocalization error). Analogously,
a system with fractional spins – ensembles of degenerate states with integer spins
– should have the same energy as the normal spin states that comprise the ensem-
ble;22 current DFA dramatically violate this condition related the strong correlation
limit (large static correlation). The self-interaction error (SIE)4,23 is also related
to the delocalization error for one-electron systems (SIE had only been defined for
one electron systems). The delocalization error concept thus supersedes the SIE
concept and is the source of many known deciencies of current DFAs: notably, the
overestimation of polarizabilities24–26 and molecular conductance,27 the incorrect
description of systems having fractional number of electrons,28 and its implications
in main group thermochemistry.29 Recently, and based on the early ideas of and
Savin,30 the so-called coulomb attenuated functionals have spawned renewed atten-
tion,19,31–33 showing improved description of systems with fractional charge.19,32
Approximate and exact Density functionals can be classified according to the
knowledge of their functional forms in terms of the electron density. Explicit den-
sity functionals are those whose functional form in terms of the electron density is
known, and their functional derivatives (with respect to the electron density) are
readily available through functional differentiation. LDA (Local density approxima-
tion) and GGA (generalized gradient approximation) functionals are all examples
of explicit functionals. Implicit density functionals, on the other hand, are function-
als whose form in terms of the electron density is not known. Orbital dependent
functionals are examples of implicit density functionals, but we emphasize that, in
principle, any density functional can be defined as an implicit density functional
through some appropriately defined wave function. The non-interacting kinetic en-
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ergy, another example of a functional not know explicitly in terms of the electron
density, can be defined in terms of the Kohn-Sham determinant (vide infra). We
have described34–38 computational approaches for the calculation of a variety of
implicit density functionals and their functional derivatives, among which we dis-
tinguish two cases. i) If a set of orbitals and an energy functional in terms of them
is known, the regularized optimized effective potential (rOEP) method is used to
evaluate the functionals derivatives. The evaluation of the exact exchange potential
from the Hartree-Fock energy functional in terms of Kohn-Sham orbitals is one ex-

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ample of the applicability of the rOEP method, but the method is general enough
that can be applied to almost any energy functional. ii) If a functional is known in
terms of Kohn-Sham orbitals but the orbitals themselves are not know, knowledge
of the electron density can be exploited to evaluate said functional through the reg-
ularized Wu-Yang method (rWY). In the process of doing so, the rWY method also
affords the functional derivative and the corresponding set of Kohn-Sham orbitals
(vide infra) that reconstruct the electron density. The need for regularization in
the OEP and WY methods originates in the fact that they are inverse ill-possed
problems.35,38–42 The regularization techniques developed for the OEP35 and WY38
methods ensure that physical solutions are obtained, and emphasize that unphys-
ical solutions41 are nothing but the controllable manifestation of their inverse
nature.
A notable example of an implicit density functional is, as mentioned above,
the Kohn-Sham kinetic energy functional Ts [ρ], which is not known as an explicit
functional of the electron density, and its computation shall be the main subject
of the present Chapter. Ts [ρ] is defined through the use of an auxiliary set of
one-electron orbitals {φi }, from which the electron density can be reconstructed
Pocc
ρ[{φi }] = i |φi |2 . This set of orbitals are the eigenstates of the Kohn-Sham
equation {T̂ + veff (r)}φi = εi φi , so the problem of determining Ts [ρ] hence be-
comes that of determining the set {φi }. Finally, Ts [ρ[{φi }]] is readily computed
as a functional of {φi }, Ts [{φi }]. The Kohn-Sham kinetic energy functional Ts [ρ]
has received considerable attention, and methods to evaluate it along with the
exchange-correlation potential have been developed over the years.37,43–49
In this work we are concerned with the direct optimization method for calcu-
lating Ts [ρ] and the Kohn-Sham potential vs (r) from electron densities,37,38 which
is quite general and applicable to arbitrary density functionals. The rWY method
utilizes a similar construction for the potential to that used in the direct optimiza-
tion method for the OEP,34 taking advantage of the variational principle in terms of
the one-electron potential v(r) alone. The Levy constrained search approach3 is re-
placed by an unconstrained optimization of the Kohn-Sham potential within a finite
basis. We introduce here for the first time an extension of the rWY method that
enables the computation of the separate exchange and correlation components of
the exchange-correlation potential by solving the OEP equation for exact exchange
after the computation of Ts [ρ] and vs (r) for a given electron density ρ(r).
U.S. or applicable copyright law.

2.2. Theory

2.2.1. Direct optimization method for the Kohn-Sham kinetic


energy functional Ts and the exact exchange-correlation
potential vxc
The Kohn-Sham kinetic energy Ts [ρ(r)] is known as an explicit functional of the
KS orbitals φi (r) and, through φi (r) ≡ φi (r)[ρ(r)], as an implicit functional of the

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Pocc.
electron density ρ(r) = i |φi (r)|2 . Ts [ρ(r)] can be defined, through Levy’s3
constrained search formulation, by resorting to an auxiliary determinantal wave-
function Ψdet. Ts [ρ] is then found by searching over all wavefunctions Ψdet for the
one that minimizes T [Ψdet]

Ts [ρ] = min T [Ψdet] , (2.1)


Ψdet →ρ

and simulateously yields ρ(r) = hΨdet |ρ̂|Ψdet i. Wu and Yang37 introduced a direct
optimization method for computing implicit density functionals that can be applied
to the computation of the Kohn-Sham kinetic energy functional. As anticipated
above, in the Wu-Y ang method Levy’s constrained search formulation3 is replaced
by an unconstrained maximization that provides a new variational principle for
Ts [ρ] in terms of the one-electron potential v(r). Consider wave functions Ψdet
whose orbitals {φi } are eigenstates of the single particle Kohn-Sham equation [T̂ +
v(r)]φi = εi φi , and hence implicit functionals of v(r) (Ψdet [v(r)]). One can then
define the following functional:
N/2
X Z
Ws [Ψdet , v(r)] = 2 hφi |T̂ |φi i + drvs (r){ρ(r) − ρin (r)} , (2.2)
i

PN/2
where ρ(r) = 2 i |φi (r)|2 . Note that it’s first derivative with respect to the
potential v(r), evaluated at the input density ρin , vanishes identically:
 
δWs [Ψdet , v(r)]
= 0, (2.3)
δv(r) ρ=ρin

and the second variation can be shown to be always non-positive:


Z
δ 2 Ws [Ψdet , v(r)]
δ 2 Ws [Ψdet , v(r)] = dr0 drδv(r0 )δv(r) ≤ 0, (2.4)
δv(r0 )δv(r)

where:
unocc.
X X occ. ∗
δ 2 Ws [Ψdet , v(r)] δρ(r) φi (r)φa (r)φ∗a (r0 )φi (r0 )
= = . (2.5)
δv(r0 )δv(r) δv(r0 ) εi − εa
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i a

Equations (2.3) and (2.4) combined imply that Ts [ρin ] is a concave functional of
v(r) and the stationary point is then a maximum. The Kohn-Sham non-interacting
kinetic energy for a given input density ρin (r) can then be determined through the
following unconstrained maximization:

Ts [ρin ] = max Ws [Ψdet [v(r)], v(r)] . (2.6)


v(r)

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The variational principle Eq. (2.6) can be turned into a direct optimization method
by choosing an appropriate expansion for the pontential. In particular, we choose
the following expansion:
X
v(r) = vext (r) + v0 (r) + bt gt (r) , (2.7)
t

where vext (r) is the external potential due to the nuclei, v0 (r) is a reference potential,
and gt (r) is a set of gaussian functions with expansions coeeficients {bt }, which are
to be determined. The problem now turns into the unconstrained maximization
of Ws [Ψdet [v(r)], v(r)] with respect to the expansion coefficients {bt }. The first
(∇b Ws ) and second derivatives (H) are readily available:
Z
∂Ws
[∇b Ws ]t = = drgt (r){ρ(r) − ρin (r)} , (2.8)
∂bt

occ unocc
X X hφi |gu (r)|φa ihφa |gt (r)|φi i
∂ 2 Ws
Hu,t = =2 + c.c. , (2.9)
∂bu ∂bt i a
εi − εa

and the maximization can be carried out efficiently with iterative optimization meth-
ods such as the quadratically convergent Newton method.50
The direct optimization approach for Ts [ρin ] can in general be extended to any
functional of the electron density (for details, the reader is referred to Ref.37 ). It
must be emphasized that the WY method relies on different variational principles
than the OEP method, every time it deals with general implicit density functionals
of the electron density. In the present case, the focus is on the KS kinetic energy of
a given density and on its exchange-correlation potential, and the value of Ws thus
represents a variational estimation of Ts .

2.2.2. Exchange vx and correlation vc components of the


exchange-correlation potential vxc

The WY procedure can be applied, as outlined above, in the computation of the


Kohn-Sham kinetic energy Ts and the exchange-correlation potential vxc (r) from a
U.S. or applicable copyright law.

given electron density ρin (r). We now present an extension that enables the com-
putation of the exchange and correlation components of the exchange-correlation
potential, which is equivalent to that used by Filippi et al.51–53 It is based in the
fact that given a set of orbitals φi (r) and eigenvalues εi , corresponding to a given
exchange-correlation potential vxc (r) and electron density ρ(r), one can solve the
so-called OEP equation for exact exchange to obtain vx (r), and obtain the pure
correlation component by difference vc (r) = vxc (r) − vx (r).
For a given electron density ρ(r) the non-interacting kinetic energy Ts [ρ] and the
exchange-correlation potential vxc (r) are obtained with the WY method as outlined

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above. The method also yields the corresponding orbitals φi (r) and orbital energies
εi . Upon convergence, the following OEP equation holds:
Z occ unocc
X X φi (r)φi (r)hj|v n` |ii
dr0 χ0 (r, r0 )vXC (r0 ) = XC
, (2.10)
i j
ε j − ε i

where χ0 (r, r0 ) is the Kohn-Sham linear response function:

δρ(r)
χ0 (r, r0 ) = , (2.11)
δvs (r0 )
n`
and vXC is the (non-local) potential that generated the input density ρin (r). The
n`
(non-local) potential vXC can be split in two contributions vxn` + vcn` , just as the
Kohn-Sham potential vxc (r) can be split into its exchange and correlation compo-
n`
nents vx (r) + vc (r). Indeed, for any vxc , we simply define vcn` (r) = vxc
n`
(r) − vxn` (r),
n`
where vx (r) corresponds to the derivative of the Hartree-Fock energy functional
with respect to the density matrix (the Hartree-Fock energy functional in terms
of the Kohn-Sham orbitals). We then solve the following OEP equation for the
exchange potential:
Z occ unocc
X X φi (r)φi (r)hj|v n` |ii
x
dr0 χ0 (r, r0 )vx (r0 ) = , (2.12)
i j
εj − εi

and compute the correlation component as:

vc (r) = vxc (r) − vx (r) , (2.13)

where vxc (r) is that of Eq. (2.7) and vx (r) comes from the solution of Eq. (2.12).
The main difficulty in the application of the above procedure in a finite basis set is
that both Eqs. (2.12) and (2.2) are inverse, ill-possed problems, and both require
regularization. Care should be taken to employ consistent regularizations schemes
in both of them.

2.3. Regularization of the WY functional


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The original work of Yang and Wu36,37 did consider a first level of regularization
for the OEP and WY methods. Indeed, a truncated singular value decomposition
(TSVD) was used for the numerically stable inversion of the Hessian matrix when
solving for the update vector p in the Newton method.50 The TSVD alone has been
shown to produce good quality potentials, with oscillations restricted to the regions
near the nuclei even when unbalanced basis sets are used.35,38 We will herein focus
on the so-called λ-regularization of the WY method, that yields potentials of the
highest quality regardless of the basis sets used, and that we refer to as the rWY

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method. For a thorough discussion of the TSVD regularization, the reader is refered
to ealier work on the subject.35–38
To effectively solve the inverse problem possed by Eq. (2.6) for the potential
and the KS kinetic energy in a stable and physically meaningful way that ensures
well behaved potentials, we have defined a regularized WY functional W̄s based on
the original WY functional Ws .37 W̄s is defined by introducing a measure of the
smoothness of the expected solution:

W̄s [Ψdet , v(r)] = Ws [Ψdet , v(r)] − λ||∇vb (r)||2 , (2.14)

where:
XX
||∇vb (r)||2 = bt bu hgt (r)| − ∇2 |gu (r)i , (2.15)
t u

is the squared norm of the gradient of the basis set expansion part of the potential
vb (r). The first and second derivatives of the regularized WY functional W̄s are
simply related to those of Ws by

∂ W̄s ∂Ws X
= − 2λ bu hgt (r)| − ∇2 |gu (r)i , (2.16)
∂bt ∂bt u
∂ 2 W̄s ∂ 2 Ws
= − 2λhgt (r)| − ∇2 |gu (r)i , (2.17)
∂bu ∂bt ∂bu ∂bt

or in the more compact matrix notation, equations (2.15), (2.16) and (2.17) read:

||∇vb (r)||2 = 2bT Tb , (2.18)


∇b W̄s = ∇b Ws − 4λTb , (2.19)
∇2b W̄s = ∇2b Ws − 4λT , (2.20)

where:

Tt,u = hgt (r)|T̂ |gu (r)i . (2.21)


U.S. or applicable copyright law.

The W̄s ({bt }) functional, as when dealing with Ws ({bt }) itself, is maximized
with respect to the expansion coefficients ({bt }) entering in the expression for the
potential. For every value of λ there corresponds an unconstrained maximum value
of W̄s , which we denote by W̄sλ = W̄s ({bλt }), whose maximizing set of coefficients are
denoted {bλt }. For such set of coefficients there corresponds a value of the Ws func-
tional, which we denote by Wsλ = Ws ({bλt }), that corresponds to the constrained
maximum for a given λ. To complete the analysis one must choose the most appro-
priate value for the λ parameter, denoted hereafter λ∗ , which is to be determined
by the L-Curve analysis,54 that we now brifly describe.

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For the L-Curve analysis one simply plots the logarithm of the solution norm,
||∇vb (r)||, against a measure of the decrease in the functional’s value due to the
additional constraint. Such a measure is given here by Ws0 − Wsλ (since Wsλ is
bounded by Ws0 , this quantity is always positive). The L-Curve plot thus represents
the trade off between the desire to fully maximize the (unconstrained) functional
and that of extracting a physically meaningful, well behaved solution.
In the classical literature of inverse problems,54 one chooses as an optimal so-
lution a value of λ∗ near the corner of the L-Curve, where the solution is already
stable with respect to variations of λ yet the trade off in the functional value is
minimum. However, the method for determining the most appropriate value for the
λ∗ chosen here is that used in our earlier work:35,38 the point along the L-Curve
with a minimum slope. We emphasize that the slope of the L-curve is given by:38
∂ log(n(λ)) ∆W (λ) ∂n(λ) (W 0 − Wsλ )
= =− s . (2.22)
∂ log(∆W (λ)) n(λ) ∂∆W (λ) n(λ)λ
Note that this analytical expression is generally applicable to L-Curve analysis. To
the best of our knowledge, was first derived in Reference.38

Fig. 2.1. (Left panel) Potentials obtained from an LDA input density of N2 using various basis
set for the potential expansion. No regularization is used. (Right panel) L-Curves for an LDA
input density of N2 using various basis sets for the potential expansion.

2.4. Results and discussion


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We present the result of applying the regularized WY method to LDA and HF


densities of N2 to obtain the KS kinetic energy and exchange-correlation potentials.
The LDA density – using the SVWN5 functional2,55,56 – was considered because
the direct availability of the exact potential through functional differentiation make
comparison with the exact result very straight forward. The Hartree-Fock (HF) den-
sity was considered to illustrate how the reliability of the regularized WY method, as
applied to the LDA case, transfers to densities generated from non-local potentials.
We also examine the case of a CCSD density of N2 , and briefly discuss other atomic

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Fig. 2.2. (Left panel) Potentials obtained from an LDA input density of N2 using various basis
set for the potential expansion. (Right panel) Potentials obtained from an LDA input density of
N2 using the UC-3 basis set for the potential expansion with different choices of λ∗ as indicated.

(Ar) and molecular systems (H2 O). Finally, we compute the exchange-correlation
potential from a CCSD density of F2 , and examine the identification of the exchange
and correlation components of the exchange-correlation potential. We have chosen
to work with a simple example for which a CCSD density can be obtained on a very
large MO basis. This make the regularization uncessesary, and removes the issue
of compatibility between the regularization schemes otherwise necessary in the two
steps of our method (Eqs. (2.6) and (2.12)).

2.4.1. Exchange-correlation vxc (r) potentials


We start by noting that the application of the WY method to a density comming
from a fully local potential displays some subtle but important differences with
respect to the case when the density comes from a non-local potential. For a given
arbitrary density ρin (r) it is in general impossible to know a priori whether it comes
from a local or non-local potential, which brings up the issue of v-representability
of the density. We note that if a density is not v-representable, the rWY method
should provide (through Ws ) the best variational estimate for the non-interacting
Kohn-Sham kinetic energy. Note also that since a non-v-representable density by
definition cannot be obtained with a local potential, one should expect a non-zero
contribution of the second term in the right-hand-side of Eq. (2.2).
U.S. or applicable copyright law.

Several basis sets are used for the potential expansion, while the cc-pVDZ basis
set has been chosen for the atomic orbitals in all cases. For HF densities, the
reference potential, v0 (r) in Eq. (2.7), corresponds to the Fermi-Amaldi potential of
a sum of atomic densities. For LDA densities, the bare coulomb potential of a sum
of atomic densities is used instead to reflect the corresponding long-range behavior.
The regularized WY method has been implemented in the NWChem program.57
We considered four different basis sets for the potential expansion in N2 . Firstly,
as an example of a balanced basis set, we have chosen the cc-pVDZ basis. Second, as
an example of unbalanced basis sets, we have considered three basis sets constructed

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from even tempered sets of s-type and p-type gaussian functions. The UC-1 basis
(for uncontracted gaussian basis 1) contains 13 s-functions (2n , −4 ≥ n ≥ 8) and
3 p-functions (2n , −2 ≥ n ≥ 0) per nitrogen atom, the UC-2 basis contains 14 s-
functions (2n , −4 ≥ n ≥ 9) and 5 p-functions (2n , −3 ≥ n ≥ 1), and the UC-3 basis
contains 18 s-functions (2n , −4 ≥ n ≥ 13) and 8 p-functions (2n , −2 ≥ n ≥ 5).
Figure 2.1 displays the unregularized potentials obtained from an LDA density
of N2 (left panel). The reader should keep in mind that these potentials con-
tain no regularization; when the WY method37 (and direct OEP method34 ) was
introduced, it contained TSVD regularization that enabled physically meaningful
potentials in most cases by eliminating all of the oscillations in the potential except
for those very close to the nuclei. We choose here to apply the λ-regularization to
unregularized-potentials (no TSVD used) to illustrate the reliability of our method.
Going back to Fig. 2.1, it is noteworthy that the larger the potential basis set, the
more oscillatory the potential becomes – an observation that carries over to all the
cases we have studies of unbalanced basis sets –. The right panel in Fig. 2.1 displays
the L-Curves obtained with the four different potential basis sets. Since Wsλ is the
variational estimate of the kinetic energy, this is the energy that should be com-
pared to the unregularized Ws0 , which is the target functional. Note that when the
atomic basis set used for the molecular orbitals is used for the potential there is no
raise in the solution norm. This indicates that no unstable, unphysical, oscillating
potential is formed for that basis set, and the basis set is hence regarded as balanced
following our earlier work.35,38 Note in this connection that the potential obtained
with this balanced basis set is not shown in Fig. 2.1, as it would show up as an
horizontal straight line due to the very large vertical scale of Fig. 2.1. Instead, said
potential can be seen in Fig. 2.2, where we note that it correlates nicely with the
actual LDA potential for N2 . The L-Curves for the UC-1, UC-2, and UC-3 basis
set do display raises in the norms and yield unphysical potentials (Fig. 2.1).
The raise in the norms in the L-Curve analysis is the defining feature of an
unbalanced basis, and we recall that we would like to choose an optimum point
along the L-Curve for which the compromise in the residual norm is minimal, yet a
well behaved potential is obtained. By a minimal compromise in the residual norm
(loss of numerical accuracy in the evaluation of the target functional) we mean the
smallest value of Ws0 − Wsλ for which the potential is well behaved. We observe
that this compromise is less than 3 × 10−4 a.u., which we expect to be beyond the
U.S. or applicable copyright law.

accuracy of the orbital basis set. Figure 2.2 also displays the potentials obtained for
the UC-3 basis set when different values are chosen for the regularization parameter
λ. This illustrates the adecuacy of the choice of λ∗ , as an smaller λ results in some
oscillations, while a large λ results in over-smoothing.

2.4.2. Kohn-Sham kinetic energy


We have so far discussed the usage of the rWY method in obtaining accurate
exchange-correlation potentials from electron densities originating in both local and

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Fig. 2.3. (Left panel) L-Curves for a HF input density of N2 using various basis sets for the
potential expansion. (Right panel) Potentials obtained from a HF input density of N2 using
various basis set for the potential expansion.

non-local potentials, exemplified by the LDA and HF cases discussed above. We


now turn to the evaluation of the Kohn-Sham kinetic energy Ts [ρ], and would like
to emphasize that the regularization process results in some loss of accuracy in the
values of the target functional. Indeed, it is a measure of that loss of accuracy that
is used in the L-Curve analysis as discussed previously. This means that even for
a density originated in a local potential, the method may not recover the kinetic
energy exactly. Consider the case of a complete basis set for the molecular orbitals.
In such case, the quality of the variational estimate for the KS kinetic energy will
increase with the size of the basis set used in the potential expansion, until the point
on which the potential basis reaches (or approximates) completeness, at which point
the variational estimate for Ts [ρ] will approach the exact value. Now consider the
case of a finite basis for the molecular orbitals, which entails certain subtleties. The
variational estimate for Ts [ρ] will improve with the size of the potential basis, up to
the point where the “MO basis/potential basis” pair becomes unbalanced. At this
point the numerical value of Ts [ρ] becomes unreliable, even though it may appear
to converge, and may lead to unphysical behaviour like, for example, reproducing
exactly the HF kinetic energy with a local potential. The KS potential itself is the
quantity one should monitor, and the onset of oscillations in it is the hallmark of an
unstable “MO basis/potential basis” pair, and regularization is needed, although it
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may result in some loss of accuracy. This loss of accuracy is the price one has to
pay to ensure the potential and KS kinetic energy remain physically meaningful. If
more accuracy is needed, the MO basis should be enlarged. It is in this way that,
as we shall see below, no potential basis can reproduce the exact KS kinetic energy
obtained originally for an LDA calculation of N2 using the cc-pVDZ basis for the
molecular orbitals. The variational estimates, however, bear comparable accuracy
to that of the MO basis itself.
Table 2.1 displays the variational estimates for the Kohn-Sham kinetic energy
obtained from and LDA density of F2 . Note that when the MO basis is used for the

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potential expansion the estimate of the KS kinetic energy is remarkably accurate,


and emphasizes the convenience of choosing a basis set for the potential that is
balanced with respect to the molecular orbital basis set. Indeed, the error in the
kinetic energy estimate is about 1·10−4 Hartree for the LDA density of N2 when the
MO basis is used for the orbital expansion, and it only increases slightly to ∼ 4·10−4
for UC-1, UC-2, and UC-3 at λ∗ . The fact that the accuracy does not increase with
the basis set size used in the potential expansion highlights the fact that the rWY
method can only give an estimate for Ts [ρ] with an intrinsic accuracy limited by
the MO basis set. Note, however, that if no regularization is used, the value of Ws0
approaches the exact value obtained from the LDA calculation and, in fact, does
get deceivingly “better” with increasing size of the potential basis set. This comes
at the expense of highly oscillatory, unphysical potentials which is not acceptable
because a physically meaningful well behaved potential is the only evidence for the
v-representability of the final density. The final density may differ slightly from
the input density, but the former is guaranteed to be v-representable, while the
latter is not. Finally, note that the estimate for Ts [ρ] depends on the regularization
parameter, and we also show in Table 2.1 how it behaves around λ∗ . As expected, a
value for λ that is too large (small) results in an estimate for Ts [ρ] that is too small
(large), and corresponds to an oversmoothed (oscillatory) potential. (Note that the
relationship between λ and the error in the kinetic energy is approximately linear.)
Table 2.2 displays the variational estimates for the Kohn-Sham kinetic energy
obtained from a HF density of N2 . Note that the unregularized results for the UC-
1, UC-2, and UC-3 potential basis get increasingly close to the HF kinetic energy,
This is unphysical because the HF density is not v-representable. This situation
is manifested in the highly oscillatory behaviour observed for the potentials in the
previous section. The estimates for Ts [ρ] when regularization is used are pretty
consistent at the optimum point in the L-Curve (λ∗ ), emphasizing the fact that, up
to the accuracy provided by the MO basis set, the regularization scheme is pretty
robust and consistent. Table 2.3 displays the results obtained for a CCSD density
of N2 using the UC-2 basis set for the potential, and we observe that the rWY best
estimate for the KS kinetic energy is below the unregularized value. Finally, we
display in Table 2.4 the variational estimated for the KS kinetic energy for LDA
and HF densities of Ar and H2 O both at the regularized and unregularized levels (for
details of these calculations, including the basis sets used and an extensive analysis
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of the potentials obtained, the reader is referred to our previous work38,58 ). In all
cases the rWY method is successful in providing consistent results not significantly
dependent on the basis sets, with the added benefit of accompanying potentials of
very high-quality that ensure the v-representability of the resulting density.

2.4.3. Exchange vx (r) and correlation vc (r) potentials


Having discussed the application of the rWY method in the computation of the
exchange-correlation potential and KS kinetic energy from electron densities, we

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Table 2.1. Variational estimates for the KS kinetic energy from an LDA (SVWN) density of N2 . Values in a.u.

MO Basis UC-1 UC-2 UC-3 LDA

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15:59
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Unregularized 108.287860859506 108.288001556831 108.288006848736 108.288007771150 108.288007771336


λ = 8 · 10−6 - 108.287905774360 108.287897445097 108.287935287901 -
λ∗ = 8 · 10−5 - 108.287573303071 108.287638341841 108.287684003632 -
λ = 8 · 10−4 - 108.282059937202 108.282301853745 108.282440788516 -

Table 2.2. Variational estimates for the KS kinetic energy from a HF density of N2 . Values in a.u.

MO Basis UC-1 UC-2 UC-3 HF


Unregularized 108.652675479578 108.654321870934 108.654602308454 108.654872594532 108.6548741907

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λ = 4 · 10−5 - 108.653436162330 108.653533237448 108.653630096598 -
λ∗ = 2 · 10−4 - 108.652151103152 108.652169778237 108.652306154364 -
λ = 1 · 10−3 - 108.642037661189 108.642098571850 108.642217629141 -

Table 2.3. Variational estimates for the KS kinetic energy from a


CCSD density of N2 . Values in a.u.

MO Basis UC-1 UC-2 UC-3


Unregularized - - 108.933404787096 -
λ = 10−5 - - 108.931139617331 -
λ∗ = 10−4 - - 108.930052082238 -
λ = 10−3 - - 108.920843011620 -
permitted under U.S. or applicable copyright law.

Table 2.4. Variational estimates for the KS kinetic energy from LDA and HF densities of Ar and H2 O. The
last column corresponds to the kinetic energy of LDA or HF the input density. Values in a.u.

MO Basis UC-1 UC-2 Input


Ar LDA Unregularized 525.750652099832 525.750661759946 525.750661759945 525.750661759945
λ∗ = 4 · 10−5 - 525.750661759945 525.750661759945 -
Ar HF Unregularized 526.708342154777 526.709052927157 526.709052927157 526.709052927157
λ∗ = 1 · 10−6 - 526.709049843973 526.709049842989 -
H2 O LDA Unregularized 75.608425385416 75.608444806071 75.608446346554 75.608446346738
λ∗ = 4 · 10−5 - 75.608395662595 75.608398121345 -

master˙16-11-12/Chp. 2
H2 O HF Unregularized 75.940200841677 75.941025308113 75.941024215260 75.941034642694
λ∗ = 2 · 10−4 - 75.939724614503 75.939732271592 -

25
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now turn to the identification of the exchange and correlation components of the
exchange-correlation potential. The application of our method is quite straightfor-
ward, and the only subtlety is that the regularization used in the iterative maximiza-
tion of Eq. (2.2) should be consistent with the regularization used in the solution of
Eq. (2.12). In order to explore the reliability of the method an attain the highest
possible accuracy in the exchange and correlation components we focus on a highly
correlated CCSD density for an atom (Be) and a small molecule (F2 ) with large
basis sets for the molecular orbitals. This effectively removes the need for regu-
larization and we observe no raise for the solution norm in the L-Curve analysis.
For Be we use a Partridge-3 basis set for the molecular orbitals (12s6p3d2f) and
an uncontracted basis set containing s-functions only for the potential expansion
(8 s-functions, exponents 47.0-0.5). For F2 we used an uncontracted version of the
aug-cc-pvTz basis set for the molecular orbitals (16s10p3d2f after removing dupli-
cate primitives) and an uncontracted basis set (6s3p1d) for the potential expansion
(exponents 2.0-64.0, 2.0-8.0, and 0.5). For the reference potential in Eq. (2.7), we
chose the Fermi-Amaldi potential.
Figure 2.4 displays the exchange-correlation potential obtained with the rWY
method, along with the exchange potential obtained by solving Eq. (2.12), and the
correlation potential obtained by difference. Note that the correlation potential
for Be is almost always negative, and compares very well with that of Filippi et
al.51 except for an extra oscillation close to the nuclei in out result. For F2 ,
we note that the exchange potential is above the exchange-correlation potential
in most of the range considered, from the bonding region (z ∼ 0) to the nuclear
region (z = 1.33a.u.) along the C∞ semiaxis. However, the exchange potential is
below the exchange-correlation potential from about z ∼ 2. This means that the
correlation potential is negative in the bonding and nuclear region, but positive for
z > 2a.u.. It remains positive throughout the numerical range considered (up to
z = 10a.u.) as seen in the right panel of Fig. 2.4, although it goes to zero fairly
quickly beyond z = 3a.u., probably as a consequence of the long-range dependence
built into the exchange and exchange-correlation potentials throught the reference
potential (v0 (r) in Eq. (2.7)).

2.5. Conclusions
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We have described the regularized Wu-Yang37,38 method (rWY) for the computa-
tion of exchange-correlation potentials and the KS kinetic energy functional, and
showed through numerical example its robustness and reliability. A modified en-
ergy functional that incorporates a measure of the smoothness of the solution is
the key ingredient in obtaining physically meaningnful potentials that ensure v-
representability of the electron densities. Any arbitrary density, possibly even non-
v-representable, can be approximated in a well defined variational sense by a v-
representable density. This also guarantees that the kinetic energy obtained indeed

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Fig. 2.4. Exchange, correlation, and exchange-correlation potentials for Be (upper panel) and F2
(lower panel).

corresponds to the KS kinetic energy, avoiding numerical artifacts that can occur
in finite basis setting. Different molecular cases have been studied with densities
obtained throught several quantum mechanical methods, illustrating the general
validity of the method. Importantly, we have here introduced for the first time an
extension to our method that allows for the computation of the separate exchange
and correlation components of the exchange-correlation potential. We anticipate
that these methods will prove helpful in the development of accurate exchange,
correlation, and kinetic energy functionals.

Acknowledgements
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Financial support from the National Science Foundation (WY) and the Office of
Naval Research (FAB) is gratefully acknowledged.

References

1. P. Hohenberg and W. Kohn, Phys. Rev. 136, B864 (1964).


2. W. Kohn and L. Sham, Phys. Rev. 140, A1133 (1965).
3. M. Levy, Proc. Natl. Acad. Sci. U.S.A. 76, 6062 (1979).

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28 F. A. Bulat & W. Yang


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4. R. G. Parr and W. Yang, Density Functional Theory of Atoms and Molecules. (Oxford
University Press, Oxford, 1989).
5. R. M. Dreizler and E. K. U. Gross, Density Functional Theory. (Springer, Berlin,
1990).
6. J. P. Perdew and Y. Wang, Phys. Rev. B. 33, 8800 (1986).
7. A. D. Becke, Phys. Rev. A. 38, 3098 (1988).
8. J. P. Perdew, Electronic Structure of Solids ’91, p. 11. Akademic, Berlin, (1991).
9. C. Lee, W.Yang, and R. G. Parr, Phys. Rev. B. 37, 785 (1988).
10. J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).
11. A. D. Becke, J. Chem. Phys. 98, 1372 (1993).
12. A. D. Becke, J. Chem. Phys. 98, 5648 (1993).
13. T. Van Voorhis and G. E. Scuseria, J. Chem. Phys. 109, 400 (1998).
14. C. Adamo and V. Barone, J. Chem. Phys. 110, 6158 (1999).
15. M. Ernzerhof and G. E. Scuseria, J.Chem. Phys. 111, 911 (1999).
16. J. Tao, J. P. Perdew, V. N. Staroverov, and G. E. Scuseria, Phys. Rev. Lett. 91,
146401 (2003).
17. A. D. Becke, J. Chem. Phys. 122, 064101 (2005).
18. P. Mori-Sánchez, A. J. Cohen, and W. Yang, J. Chem. Phys. 124, 091102 (2006).
19. A. J. Cohen, P. Mori-Sánchez, and W. Yang, J. Chem. Phys. 126, 191109 (2007).
20. A. J. Cohen, P. Mori-Sánchez, and W. Yang, Science. 312, 792 (2008).
21. P. Mori-Sánchez, A. J. Cohen, and W. Yang, Phys. Rev. Lett. 102, 066403 (2009).
22. A. J. Cohen, P. Mori-Sánchez, and W. Yang, J. Chem. Phys. 129, 121104 (2008).
23. J. P. Perdew and A. Zunger, Phys. Rev. B. 23(10), 5048 (1981).
24. B. Champagne, E. A. Perpète, S. J. A. van Gisbergen, E.-J. Baerends, J. G. Snijders,
C. Soubra-Ghaoui, K. A. Robins, and B. Kirtman, J. Chem. Phys. 109, 10489 (1998).
25. P. Mori-Sánchez, Q. Wu, and W. Yang, J. Chem. Phys. 119, 11001 (2003).
26. F. A. Bulat, A. Toro-Labbé, B. Champagne, B. Kirtman, and W. Yang, J. Chem.
Phys. 123, 014319 (2005).
27. S.-H. Ke, H. U. Baranger, and W. Yang, J. Chem. Phys. 126, 201102 (2006).
28. Y. Zhang and W. Yang, J. Chem. Phys. 109, 2604 (1998).
29. E. R. Johnson, P. Mori-Sánchez, A. J. Cohen, and W. Yang, J. Chem. Phys. 129,
204112 (2008).
30. A. Savin, Recent Developments and Applications of Modern Density Functional The-
ory, p. 327. Elsevier, Amsterdam, (1996).
31. H. Iikura, T. Tsuneda, T. Yanai, and K. Hirao, J. Chem. Phys. 115, 3540 (2001).
32. P. Mori-Sánchez, A. J. Cohen, and W. Yang, J. Chem. Phys. 125, 201102 (2006).
33. O. A. Vydrov and G. E. Scuseria, J. Chem. Phys. 125, 234109 (2006).
34. W. Yang and Q. Wu, Phys. Rev. Lett. 89, 143002 (2002).
35. T. Heaton-Burgess, F. A. Bulat, and W. Yang, Phys. Rev. Lett. 98, 256401 (2007).
36. Q. Wu and W. Yang, J. Theo. Comp. Chem. 2, 627 (2003).
U.S. or applicable copyright law.

37. Q. Wu and W. Yang, J. Chem. Phys. 118, 2498 (2003).


38. F. A. Bulat, T. Heaton-Burgess, A. J. Cohen, and W. Yang, J. Chem. Phys.. 127,
174101 (2007).
39. S. Hirata, S. Ivanov, I. Grabowski, R. J. Bartlett, K. Burke, and J. D. Talman, J.
Chem. Phys. 115, 1635 (2001).
40. A. Ben-Haj-Yedder, E. Cances, and C. Le Bris, Diff. Int. Eq. 17, 331 (2004).
41. V. N. Staroverov, G. E. Scuseria, and E. R. Davidson, J. Chem. Phys. 124, 141103
(2006).
42. E. Cances, G. Stoltz, G. E. Scuseria, V. N. Staroverov, and E. R. Davidson, MathS
In Action. 2, 1 (2009).

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43. Q. Zhao and R. G. Parr, Phys. Rev. A. 46, 2337 (1992).


44. Q. Zhao and R. G. Parr, J. Chem. Phys. 98, 543 (1993).
45. Q. Zhao, R. C. Morrison, and R. G. Parr, Phys. Rev. A. 50, 2138 (1994).
46. V. E. Ingamells and N. C. Handy, Chem. Phys. Lett. 248, 373 (1996).
47. D. J. Tozer, V. E. Ingamells, and N. C. Handy, J. Chem. Phys. 105, 9200 (1996).
48. D. J. Tozer, K. Somasundram, and N. C. Handy, Chem. Phys. Lett. 265, 614 (1997).
49. D. J. Tozer, N. C. Handy, and P. Palmieri, Mol. Phys. 91, 567 (1997).
50. W. H. Press, S. A. Teukolsky, W. T. Vetterling, and B. P. Flannery, Numerical Recipes
in FORTRAN: The Art of Scientific Computing. (Cambridge University Press, Cam-
bridge, 1992).
51. C. Filippi, C. J. Umrigar, and X. Gonze, Phys. Rev. A. 54, 4810 (1996).
52. A. Görling and M. Levy, Phys. Rev. A. 50, 196 (1994).
53. A. Görling and M. Levy, Int. J. Quantum Chem., 56(S29), 93 (1995).
54. P. C. Hansen, Rank-Deficient and Discrete Ill-Posed Problems: Numerical Aspects of
Linear Inversion. (Society for Industrial and Applied Mathematics, Philadelphia, PA,
1998).
55. J. C. Slater, Quantum Theory of Molecules and Solids. (McGraw-Hill, New York,
1974).
56. S. H. Vosko, L. Wilk, and M. Nusair, Can. J. Phys. 58, 1200 (1980).
57. E. Apra, E. J. Bylaska, W. de Jong, M. T. Hackler, S. Hirata, L. Pollack, D. Smith,
T. P. Straatsma, T. L. Windus, R. J. Harrison, J. Nieplocha, V. Tipparaju, M. Ku-
mar, E. Brown, G. Cisneros, M. Dupuis, G. I. Fann, H. Fruchtl, J. Garza, K. Hi-
rao, R. Kendall, J. A. Nichols, K. Tsemekhman, M. Valiev, K. Wolinski, J. Anchell,
D. Bernholdt, P. Borowski, T. Clark, D. Clerc, H. Dachsel, M. Deegan, K. Dyall, D. El-
wood, E. Glendening, M. Gutowski, A. Hess, J. Jaffe, B. Johnson, J. Ju, R. Kobayashi,
R. Kutteh, Z. Lin, R. Littlefield, X. Long, B. Meng, T. Nakajima, S. Niu, M. Ros-
ing, G. Sandrone, M. Stave, H. Taylor, G. Thomas, J. van Lenthe, A. Wong, , and
Z. Zhang. NWChem, A Computational Chemistry Package for Parallel Computers,
Version 4.5., (2003). Pacific Northwest National Laboratory, Richland, Washington
99352-0999, USA. A modified version.
58. F. A. Bulat, T. Heaton-Burgess, A. J. Cohen, and W. Yang, EPAPS Document No.
E-JCPSA6-127-308742. (2007).
U.S. or applicable copyright law.

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Chapter 3

The Single-Particle Kinetic Energy of Many-Fermion Systems:


Transcending the Thomas-Fermi plus Von Weizsäcker Method

G. G. N. Angilella1 and N. H. March2


1
Dipartimento di Fisica e Astronomia, Università di Catania and INFN
Sez. Catania, and CNISM, Sez. Catania, 64
Via S. Sofia, I-95123 Catania, Italy
and Scuola Superiore di Catania, Università di Catania
5/i, Via S. Nullo, I-95123 Catania, Italy
2
Donostia International Physics Center (DIPC)
E-20018 San Sebastian/Donostia, Spain
and Oxford University, Oxford, UK and
Department of Physics, University of Antwerp
B-2020 Antwerp, Belgium

After a short introduction to the semiclassical Thomas-Fermi (TF) method, and


the gradient correction to its kinetic energy term proposed by von Weizsäcker
(vW), some attention is given to the differential form of the virial theorem. In
one dimension, this allows the kinetic energy to be determined from the ground-
state Fermion density ρ(r) generated by a given potential V (r). This is followed
by a summary of the perturbative expansion of the Dirac density matrix γ(r, r0 ) in
powers of the given three-dimensional potential V (r). This, following March and
Murray, is shown, when r0 = r, to sum to the TF density-potential relation when
V (r) varies only slowly in configuration space. A corresponding treatment of the
kinetic energy density t(r) follows. Due to the interest in experiments in ultracold
Fermion vapours, the case of harmonic confinement of independent Fermions is
next summarized. In one dimension, the kinetic energy functional T [ρ] is known,
and has as building blocks the TF form ρ3 (r) and the vW gradient correction
term ρ02 (r)/ρ(r), even though T [ρ] is itself fully non-local in this example. For
D dimensions and an arbitrary number of closed shells, the differential equation
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for the density is summarized, together with an explicit expression for the kinetic
energy density as a functional of the Fermion ground-state density. The concept
of the Pauli potential is then referred to, in relation to the functional density
δT [ρ]/δρ(r) for a general potential V (r). As an example, the Pauli potential is
given explicitly for the case of harmonically confined independent Fermions.
A brief section notes some significant generalizations when the potential V (r)
of density functional theory is replaced by the non-local generalization V (r, r0 ),
the most important case of this latter form being Hartree-Fock theory.

31

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32 G. G. N. Angilella & N. H. March


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Contents
3.1 Background and outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.2 Fermions in surface regimes: nuclei and simple liquid metals . . . . . . . . . . . . . . . 34
3.2.1 The nucleon surface density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.2.2 Brief background on surface energies . . . . . . . . . . . . . . . . . . . . . . . . 35
3.3 Variational principle for the TF plus von Weizsäcker (TFvW) method . . . . . . . . . 35
3.4 Differential virial theorem and the Dirac density matrix . . . . . . . . . . . . . . . . . 36
3.4.1 Relation of the exact DVT to the semiclassical Thomas-Fermi method . . . . . 38
3.5 Perturbative expansion of Dirac density matrix γ(r, r0 ) in powers of the given one-body
potential V (r) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.5.1 Stoddart-March series for the kinetic energy density t(r) in three dimensions . . 40
3.6 Complete DFT for harmonically confined Fermions in D dimensions, for an arbitrary
number of closed shells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.6.1 Current experimental focus on many Fermions that are harmonically confined . 40
3.6.2 Differential equation for Fermion density . . . . . . . . . . . . . . . . . . . . . 41
3.6.3 Kinetic energy density functional t[ρ] for arbitrary number of Fermions moving
independently in one-dimensional harmonic oscillator potential . . . . . . . . . 41
3.6.4 Summary of complete DFT for many closed shells of Fermions which are (isotrop-
ically) harmonically confined in D dimensions . . . . . . . . . . . . . . . . . . . 42
3.7 The Pauli potential in relation to the functional derivative of the single-particle kinetic
energy density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.7.1 Relation to the differential virial theorem . . . . . . . . . . . . . . . . . . . . . 43
3.7.2 Example of harmonic confinement . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.8 Non-local potential theory: V (r) 7→ V (r, r0 ) . . . . . . . . . . . . . . . . . . . . . . . . 44
3.8.1 Fine-tuning of Hartree-Fock (HF) density for spherical atoms like neon . . . . . 45
3.8.2 Scaling approach to obtain a correlated density ρ(r) from HF densities for Ne
and Ar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.9 Summary and directions for future studies . . . . . . . . . . . . . . . . . . . . . . . . . 47
A.1 Exact correlated kinetic energy related to Fermion density in model two-electron atom
with harmonic confinement and arbitrary interparticle interaction . . . . . . . . . . . 48
A.1.1 Correlated relative motion kinetic energy density, in terms of relative motion
wave function ΨR (r) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
A.1.2 Some specific results for correlated kinetic energy of model two-electron ground
states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
A.2 Transcending the von Weizsäcker single-particle kinetic energy in an artificial two-
electron atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

3.1. Background and outline

Modern density functional theory (DFT) has its origins in the so-called Thomas-
Fermi-Dirac (TFD) statistical theory, reviewed by Gombás1 and by March.2,3
U.S. or applicable copyright law.

Nowadays, the TFD method is viewed, in modern parlance, as a completely local


density approximation. This means that not only are exchange (x) and correlation
(c) approximated via the homogeneous electron liquid (jellium model — see e.g.
Ref. 4), with its constant electron density, ρ0 say, replaced by the inhomogeneous
density ρ(r) in the molecules, clusters or condensed phases under consideration, but
also, and now involving a much more serious approximation, the single-particle (s)
kinetic energy density functional, Ts [ρ] say, is written as3
Z  2/3
TFD 5/3 3h2 3
Ts [ρ] = ck ρ (r) dr, ck = . (3.1)
10m 8π

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Already, it was known to von Weizsäcker5 that Eq. (3.1) needed to be corrected in
systems with electron density ρ(r) varying strongly in space (e.g. the Fermions in
the nuclear surface, or the electrons at the surface of a simple liquid metal: to be
considered briefly below), by a term having the form
Z
~2 (∇ρ(r))2
TsvW [ρ] = dr. (3.2)
8m ρ(r)
One major focus of this review is to assess the continuing usefulness of the forms
(3.1) and (3.2) as building blocks in ongoing research to construct the correct single-
particle kinetic energy functional Ts [ρ]. As discussed at length, e.g. in Parr and
Yang,6 in the usual DFT programmes currently employed in practical studies on
molecules and condensed phases, Ts [ρ] is bypassed by going back to symmetrized
Hartree-like orbitals (the so-called Slater-Kohn-Sham (SKS) orbitals 7,8 ), and calcu-
lating the single-particle kinetic energy by standard quantum-mechanics using wave
functions determined from an appropriate one-body Schrödinger equation. Authors
who use this wave function approach often refer to work on constructing Ts [ρ] as
‘orbital-free’ DFT.
With this brief historical introduction, the outline of the present review is as fol-
lows. In a brief section 3.2, we shall expand on the relevance of Eqs. (3.1) and (3.2)
for the treatment of (a) the Fermions in the nuclear surface, and (b) the electrons
in a liquid metal surface. We shall also there take the opportunity of noting the
limited accuracy of the Fermion density in both applications (a) and (b), when we
use the Thomas-Fermi (TF) plus the von Weizsäcker approximation to the single-
particle kinetic energy in a variational framework. Then in section 3.4 we shall
introduce the so-called differential virial theorem derived, via the so-called Dirac
density matrix (equivalent to an off-diagonal Fermion density), in one dimension
by March and Young.9 This will be related to the TF result in one dimension.
The restriction to one dimension will then be relaxed in section 3.5. There, results
are recorded from an infinite order perturbation treatment in three dimensions,
based on the free-particle Dirac density matrix10 as the unperturbed problem will
be presented, the resulting perturbation series having been given to all orders in
a one-body potential energy V (r) by March and Murray.11 As these authors then
showed, this series sums to the TF density-potential relation when V (r) varies by
but a small fraction of itself over a characteristic Fermion wavelength. Correspond-
U.S. or applicable copyright law.

ingly, the single-particle kinetic energy, derived from the Dirac matrix by Stoddart
and March12 to all orders in V (r), sums to the TF limiting local density approxi-
mation (LDA) when the TF ρ-V relation is used. Because of experimental interest
on ultracold atomic gases of Fermions, a complete DFT of Ts [ρ] for harmonically
confined Fermions is then set out in section 3.6, beginning for simplicity of presen-
tation with the one-dimensional case. For the subsequent generalization to three
dimensions, it is pointed out that the March-Murray series for ρ[V ] can be summed
exactly for a harmonic confinement one-body potential V (r), as well as t[V ] for
the kinetic energy density. Section 3.8 describes how the differential virial theorem

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0.8
ρ / ρ0

0.6

0.4

0.2

0
-6 -4 -2 0 2 4 6
kx
Fig. 3.1. Nucleon density close to the nuclear surface, within a semiempirical statistical model.13
Redrawn from Ref. 14.

(DVT), and the corresponding force-balance equation which follows directly from
the DVT, can be derived for a three-dimensional Hamiltonian with given external
potential and general inter-Fermion two-body interactions. Section 3.9 constitutes
a summary plus some proposed directions for future research on Ts [ρ] which should
prove fruitful. Some Appendices report on the correction of Ts [ρ] to embrace cor-
relation kinetic energy, in solvable models.

3.2. Fermions in surface regimes: nuclei and simple liquid metals

As anticipated, we report below the relevance of TF and von Weizsäcker ‘building


blocks’ to Ts [ρ] in discussing (a) Fermions in the nuclear surface region, and (b)
simple liquid metal surfaces.

3.2.1. The nucleon surface density


U.S. or applicable copyright law.

We appeal here to the early work of Berg and Wilets15,16 and to the review article
by Wilets.14 In this latter study, Wilets records a semiempirical statistical model
based on equal numbers of neutrons and protons and with neglect of Coulomb forces.
Figure 3.1 has been redrawn from Ref. 12 and shows an independent particle model
using a semi-infinite well with a sloping wall, following Swiatecki.13 The Fermi
energy is taken to be 32.5 MeV and the wave number k appearing in the plot is
1.25 fm−1 . The solid and dashed curves of Fig. 3.1 reveal oscillations (the so-called
Friedel oscillations) while the dotted curve shows the TF approximation. This
TF method, being semiclassical, is, roughly speaking, akin to geometrical optics

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compared with wave optics, and so it fails to show any of the oscillatory (diffraction)
effects revealed in the solid curve of Fig. 3.1.

3.2.2. Brief background on surface energies


3.2.2.1. Nucleon surface energies

Berg and Wilets15,16 used the TF method plus a modified form of the von Weizsäcker
correction displayed in Eq. (3.2) to estimate surface energies of nuclei. Essentially,
these authors wrote the ground-state energy E of the nucleus in the approximate
form
Z  
λ~2 (∇ρ)2
E= (ρ) + dr, (3.3)
8m ρ
where (r) is a local, TF-like contribution, while the second term of the right-hand
side is of the form of von Weizsäcker, m being now the nucleon mass, reduced by
the factor λ. Then in a semi-infinite nuclear model, the surface energy is shown by
Berg and Wilets14–16 to have the form
Z
λ~2 ∞ 0 2
(u ) dx, (3.4)
m −∞

with u = ρ1/2 , often referred to below as the density amplitude.

3.2.2.2. Application to a liquid metal planar surface


Independently, Brown and March17 used a closely related method to discuss the
surface energy σ of simple liquid metals, as well as to estimate the ‘thickness’, `
say, of the liquid-vapour interface. Their main result is that

σ = κ−1
T `, (3.5)

where κT is the isothermal compressibility of the bulk liquid metal. Returning to


Eq. (3.4), the thickness ` involves the parameter λ, reducing the von Weizsäcker
‘inhomogeneity’ kinetic energy Eq. (3.2) as well as the Fermi energy of the liquid
metal. For further details reference may be made to the review article by Brown
U.S. or applicable copyright law.

and March.18

3.3. Variational principle for the TF plus von Weizsäcker


(TFvW) method

The basic variational principle on which the TFvW method is founded takes the
form

δ(E − N µ) = 0 (3.6)

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where the variation δ is with respect to the density ρ(r). In turn the number of
Fermions N is related to ρ(r) by
Z
N = ρ(r)dr. (3.7)

For a given one-body potential energy V (r), this yields, on insertion of the ki-
netic
R energy given as the sum of Eqs. (3.1) and (3.2), plus the potential energy
ρ(r)V (r)dr, for the energy E in Eq. (3.6)

5 δT vW
µ= ck ρ2/3 (r) + s + V (r). (3.8)
3 δρ(r)
Although µ was introduced into the variational principle Eq. (3.6) as a Lagrange
multiplier to take care of the density normalization Eq. (3.7), Eq. (3.6) is readily
recognized as the statement that the chemical potential µ of the inhomogeneous
Fermi assembly described by the TFvW method for a given one-body potential
V (r) is the same at every point in the Fermion density distribution ρ(r).3 For a
full generalization of Eq. (3.8) which removes the limitation to the TFvW method,
the reader is referred to the book by Parr and Yang.6 The functional derivative
δTsvW /δρ(r) is readily derived from Eq. (3.2) to insert in Eq. (3.8) but we need not
give the details at this point.

3.4. Differential virial theorem and the Dirac density matrix

At this point, we shall introduce the differential virial theorem as derived in one
dimension by March and Young19 using the so-called equation of motion of the
Dirac density matrix. Although the spirit of this review concerns what is now
termed ‘orbital-free’ DFT, let us note that a specified potential V (r) generates the
ground-state density ρ(r) from orbitals, say ψi (r), given by the Schrödinger equation
2m
∇2 ψi (r) + [i − V (r)]ψi (r) = 0. (3.9)
~2
The ground-state density ρ(r) is then given by the sum of the squares of the lowest
N normalized orbitals ψi (r) via
N
X
U.S. or applicable copyright law.

ρ(r) = ψi (r)ψi∗ (r). (3.10)


i=1

Dirac10 introduced the ‘off-diagonal’ density γ(r, r0 ) by writing


N
X
γ(r, r0 ) = ψi (r)ψi∗ (r0 ), (3.11)
i=1

which is evidently such that γ(r, r0 )|r0 =r = ρ(r) by comparison with Eq. (3.10). Em-
ploying the Schrödinger equation (3.9), it is a quite straightforward matter to form

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the difference ∇2r γ(r, r0 ) − ∇2r0 γ(r, r0 ), which enables the one-electron eigenvalues
i to be removed and is readily shown to be given by
2m
∇2r γ(r, r0 ) − ∇2r0 γ(r, r0 ) = [V (r) − V (r0 )]γ(r, r0 ). (3.12)
~2
This is the equation of motion for the Dirac density matrix γ(r, r0 ) for electrons of
mass m moving in a given one-body potential energy V (r).
In early work, March and Young9 utilized Eq. (3.12) in one dimension to de-
rive the so-called differential virial theorem (DVT), which will be a theme running
through this present review. Writing the density matrix as γ(ξ, η), where
x + x0 x − x0
ξ= , η= , (3.13)
2 2
reduces the one-dimensional form of Eq. (3.12) to read
∂2 2m
γ(ξ, η) = 2 [V (ξ + η) − V (ξ − η)]γ(ξ, η). (3.14)
∂ξ∂η ~
If we define the kinetic energy per unit length from the Schrödinger equation as
−(~2 /2m)ψi d2 ψi /dx2 for the wave function ψi , then summing over i from 1 to N
we obtain the result of March and Young9 that
∂t(x) 1 ∂V 1 ∂3ρ
=− ρ − (3.15)
∂x 2 ∂x 8 ∂x3
by expansion of Eq. (3.14) around the diagonal x0 = x corresponding to η = 0. In
Eq. (3.15) t(x) is evidently given by
N
~2 X ∂2
t(x) = − ψi (x) 2 ψi∗ (x), (3.16)
2m i=1 ∂x

which is readily rewritten in terms of the one-dimensional Dirac density matrix as



~2 ∂ 2
0
t(x) = − 2
γ(x, x ) . (3.17)
2m ∂x x0 =x

While the focus of the present review is to obtain t(x) in terms of the ground-state
density ρ(x) — an aim so far achieved completely only for specific forms of the one-
body potential V (x) — it is to be emphasized from Eq. (3.17) that the ‘off-diagonal’
U.S. or applicable copyright law.

density γ(x, x0 ) is the natural tool to use in obtaining t(x).


Next, let us very briefly explain why Eq. (3.15) is termed a ‘differential’ virial
theorem (DVT). First, to form the so-called virial of Clausius, essentially r · F
in three dimensions, where F is the force −∂V (r)/∂r, let us multiply Eq. (3.15)
throughout by x and integrate from −∞ to ∞. Then integration by parts readily
yields
Z ∞ Z
1 ∞
T = t(x)dx = xF (x)ρ(x)dx, (3.18)
−∞ 2 −∞

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or
2T = hxF (x)i. (3.19)
With T evidently being the total kinetic energy and the brackets representing a
quantum-mechanical average, we have regained the quantum version of the virial
theorem of Clausius.
Already, Eq. (3.15) is seen to allow, by quadrature with suitable physical bound-
ary conditions, the kinetic energy t(x) to be determined directly, for N Fermions,
from the given one-body potential V (x) plus the ground-state density ρ(x) which
it generates.

3.4.1. Relation of the exact DVT to the semiclassical


Thomas-Fermi method
The semiclassical TF method is founded in Fermi statistics and is most appropriate
when the number of particles N is large. Then it is easy to rewrite the chemical
potential Eq. (3.8) in one dimension, and to obtain
µTF = 3cD=1
k ρ2TF (x) + V (x) (3.20)
if we neglect the von Weizsäcker term, as is increasingly appropriate as N becomes
very large. Here, cD=1
k is known from free Fermi gas theory, and corresponding to
Eq. (3.20) it is easy to show that
tTF (x) = cD=1
k ρ3TF (x), (3.21)
the general D-dimensional TF result being proportional to ρ1+2/D (r). To make
contact with the exact DVT in Eq. (3.15), let us next differentiate Eq. (3.21) to
find
∂tTF (x) ∂ρTF
= 3cD=1
k ρ2TF (x) . (3.22)
∂x ∂x
But from Eq. (3.20) we have
ρ2TF = const × [µTF − V (x)] (3.23)
and hence, since µTF is independent of x,
U.S. or applicable copyright law.

∂ρTF ∂V (x)
2ρTF = const × . (3.24)
∂x ∂x
Substituting Eq. (3.24) into Eq. (3.22) we find almost immediately that
∂tTF (x) ∂V (x)
= const × ρTF (x) (3.25)
∂x ∂x
and the constant, from free Fermi gas theory, turns out to be − 21 . Thus, Eq. (3.25)
relates to the exact DVT result Eq. (3.15) by neglect of ∂ 3 ρ/∂x3 . This neglect is
due to the fact that the TF approximation uses free Fermi gas relations locally,

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and is therefore valid for slowly varying potentials V (x) and hence slowly varying
densities ρ(x).
We are therefore encouraged to summarize in the following section a perturbative
treatment of the Dirac density matrix γ(r, r0 ) in three dimensions, following the
early study of March and Murray,11 which removes the TF constraint of slowly
varying potentials V (r).

3.5. Perturbative expansion of Dirac density matrix γ(r, r0 ) in


powers of the given one-body potential V (r)

March and Murray11 switched the potential V (r) on to a three-dimensional uniform


Fermi gas with density ρ0 and Fermi wave number kF given by
kF3
ρ0 = . (3.26)
3π 2
With plane waves exp(ik · r) as the orbitals, the free gas density matrix γ0 (r, r0 ) is
readily calculated as19
kF3 j1 (kF |r − r0 |)
γ0 (r, r0 ) = , (3.27)
π 2 kF |r − r0 |
where j1 (x) = (sin x − x cos x)/x2 is the first-order spherical Bessel function. Evi-
dently, when r0 = r, Eq. (3.27) reduces to Eq. (3.26). While γ(r, r0 ) − γ0 (r, r0 ) was
given to all orders in V (r), we quote here only the O(V ) result, which reads11
Z
k2 V (r1 ) j1 (kF |r − r1 | + kF |r1 − r0 |)
γ(r, r0 )−γ0 (r, r0 ) = − F2 dr1 +O(V 2 ). (3.28)
2π 2π |r − r1 | |r1 − r0 |
By analogy with the TF statistical method, we shall focus below on the diagonal
element ρ(r) − ρ0 = [γ(r, r0 ) − γ0 (r, r0 )]r0 =r , and the corresponding kinetic energy
density calculated subsequently by Stoddart and March.12
Then we can write, following March and Murray,11

X
ρ(r) − ρ0 = ρj (r), (3.29)
j=1

where ρj (r) is O(V j ) and is known explicitly in terms of kF , V (r) and the spherical
U.S. or applicable copyright law.

Bessel function j1 (x) given above.


What March and Murray11 proved was that in the limit when V (r) was slowly
varying in space, Eq. (3.29) summed to precisely the TF density-potential rela-
tion. To date, however, Eq. (3.29) has only been summed exactly for one other
case, namely when V (r) = 21 kr2 . This is however the important physical case of
harmonic confinement, to be treated at some length in the following section. To
summarize at this point, we can say that the perturbative series of March and Mur-
ray in Eq. (3.29) represents an exact quantum-mechanical generalization of the TF
semiclassical method.

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3.5.1. Stoddart-March series for the kinetic energy density t(r) in


three dimensions
Since the Dirac density matrix γ(r, r0 ), as outlined above, is known exactly to all
orders in a given one-body potential V (r), we can use the exact formula
~2 2
t(r) = − ∇r γ(r, r0 ) r0 =r (3.30)
2m
to calculate the kinetic energy density difference t(r)−t0 corresponding to Eq. (3.29)
for the particle density. The result obtained by Stoddart and March12 takes the
remarkably simple form
X∞  
j
t(r) − t0 = −V (r) ρj (r), (3.31)
j=1
j+1
where ρj (r) enters the density Eq. (3.29). It seems natural enough then to rewrite
Eq. (3.31) in the equivalent form
X∞ X∞
1
t(r) − t0 = −V (r) ρj (r) − V (r) ρj (r)
j=1 j=1
j + 1

X 1
= −V (r)[ρ(r) − ρ0 ] − V (r) ρj (r). (3.32)
j=1
j+1
Thus, as in the one-dimensional DVT in Eq. (3.15), both ρ(r) and V (r) enter.
For the special case of harmonic confinement, the summation in Eq. (3.32) can be
completed, and hence an exact generalization of the TF method for kinetic energy
density can be achieved in this physically important example, to which we now turn.

3.6. Complete DFT for harmonically confined Fermions in D


dimensions, for an arbitrary number of closed shells

In this section, we will briefly review a complete DFT for independent harmoni-
cally confined Fermions in D dimensions. Let us begin by emphasizing the current
experimental interest in this area.

3.6.1. Current experimental focus on many Fermions that are


harmonically confined
U.S. or applicable copyright law.

It is worth stressing at this point that many harmonically confined Fermions are
currently of major interest because of experiments on ultracold vapours of 40 K
and 6 Li isotopes populating hyperfine states inside magnetic traps.20 For these
experiments based on axially symmetric magnetic traps, it proves possible to range
from a fully spherical three-dimensional trap to a quasi-two-dimensional system.
This motivated the treatment of harmonic confinement in D dimensions summarized
below. It will be useful first of all to discuss, somewhat intuituively, the one-
dimensional case, going back to the work of Lawes and March.21

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3.6.2. Differential equation for Fermion density


We shall consider more generally the functional derivative δT /δρ(x) of the kinetic
energy T but intuitively (cf. the Thomas-Fermi method)
 −1
δT ∂t ∂ρ
∼ . (3.33)
δρ(x) ∂x ∂x
Now, from Eq. (3.6) it follows that δT /δρ(x) = µ − V (x), and hence, employing
Eq. (3.33), we find
∂t ∂ρ ∂ρ
+ V (x) =µ . (3.34)
∂x ∂x ∂x
Substituting for ∂t/∂x from the differential virial theorem (DVT), Eq. (3.15), we
then find
1 ∂V 1 ∂ρ ∂ρ
− ρ − ρ000 (x) + V (x) =µ . (3.35)
2 ∂x 8 ∂x ∂x
As Lawes and March proved,21 making use of solvable harmonic oscillator (HO)
wave functions, Eq. (3.35) is exact if µ = N , the lowest nodeless wave function
corresponding to N = 1.
Thus, for arbitrary N , we no longer need the Schrödinger equation for harmon-
ically confined Fermions in one dimension in order to calculate: (a) the particle
density in the ground state, and (b) hence the kinetic energy per unit length t(x).
However, it is instructive to get T [ρ] explicitly for harmonic confinement.

3.6.3. Kinetic energy density functional t[ρ] for arbitrary number


of Fermions moving independently in one-dimensional
harmonic oscillator potential
By combining the DVT (arbitrary V ) and the Lawes-March differential equation
(3.35), which is however only true for one-dimensional harmonic confinement, one
can show22 that
t(x) = tvW (x) + ξ(x)tTF (x), (3.36)
where
1 ρ02
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tvW (x) = (3.37)


8 ρ
and
Z "  0 #
x
4 t0 (x) tvW (x)
ξ(x) = ξ(0) + dx vW − , (3.38)
3 0 tTF (x) tTF (x)

with tTF (x) = const × ρ3 (x) in 1D and tTF (r) = const × ρ1+2/D (r) in arbitrary
dimensions D (LDA). Thus it is possible to construct the x-dependence of the exact
t(x) solely from the Thomas-Fermi plus von Weizsäcker kinetic energy ‘densities’

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(viz. energy per unit length, in one dimension) as building blocks. One can also
get for the isotropic harmonic oscillator and M closed shells a complete DFT for
arbitrary M .

3.6.4. Summary of complete DFT for many closed shells of


Fermions which are (isotropically) harmonically confined in
D dimensions

First of all, the differential equation for M + 1 closed shells is23


  
~2 ∂ 2 1 D ∂V
∇ ρ(r) + M + ~ω − V (r) ρ0 (r) + ρ(r) = 0, (3.39)
8m ∂r 2 2 ∂r

where V (r) = 21 mω 2 r2 , and ∇ denotes the D-dimensional gradient.


Secondly, the kinetic energy ‘density’ t(r) in D dimensions is
Z r
D ρ1+2/D (r) ρ1+2/D (r) 1 ∂ 2 ~2 ∇2 ρ(r)
t(r) = µ 2/D + ∇ ρ ds − , (3.40)
D+2 ρ (0) 4(D + 2) 0 ρ1+2/D ∂s 4m D + 2

where the chemical potential µ for M + 1 closed shells is given by


 
1
µ = M + (D + 1) ~ω. (3.41)
2

Of course, Eq. (3.39) leads back to the Lawes-March21 one-dimensional equation,


and Eq. (3.40) becomes the March et al.22 result for t(x) when D = 1.

3.7. The Pauli potential in relation to the functional derivative of


the single-particle kinetic energy density

Having ‘seeds’ in the early study of March and Murray,11 the background to the
introduction of the Pauli potential, denoted below by VP (r), into DFT has been
well reviewed by Levy and Görling24 (see also Ref. 25). As noted by one of us,26,27
the problem of developing an adequate approximation to the single-particle kinetic
energy functional Ts [ρ] can be viewed as equivalent to finding a useful approximation
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to the Pauli potential VP (r).


In essence, one can regard the introduction of VP (r) as a ‘bosonization’ of a
many-body potential V (r). Therefore, one writes a Schrödinger-like equation for
the so-called ground-state density amplitude ρ1/2 (r), with V (r) modified by the
addition of the Pauli potential VP (r). Thus one has
2m
∇2r ρ1/2 (r) + [I − V (r) − VP (r)]ρ1/2 (r) = 0, (3.42)
~2
where I is the ionization potential.

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3.7.1. Relation to the differential virial theorem


Below, we follow the recent study of March and Nagy28 in combining the Pauli
potential theory with the differential virial theorem (DVT), already introduced in
section 3.4 [see especially Eq. (3.15) for the general one-dimensional form].
We next invoke the three-dimensional form of the differential virial theorem
derived by Holas and March.29 This now involves the kinetic energy density tensor
tαβ (r) rather than just t(x) appearing in Eq. (3.15) of the one-dimensional case.
Then the vector field zs (r) defined by Holas and March29 has components
X ∂ (s)
zs(α) (r) = 2 t (r), (3.43)
∂rβ αβ
β

and the single-particle (s) DVT then corresponds in three dimensions to the force
balance equation, which we write in spherical symmetry only, and which then reads
∂V (r) ~2 ∂ 2 r̂ · zs (r)
− =− ∇ ρ(r) + , (3.44)
∂r 4mρ(r) ∂r ρ(r)
where r̂ denotes the unit radial vector, r̂ = r/r. March and Nagy28 have more
recently shown that in the above case of spherical symmetry considered in Eq. (3.44),
the final term could be replaced by a form involving the first derivative of the Pauli
potential VP (r), namely
 
r̂ · zs (r) 4 tvW 1 ∂tvW
= + + VP0 (r). (3.45)
ρ(r) ρ(r) r 2 ∂r
With reference to Eq. (3.45), Akbari et al.30,31 gave the first term on the right-hand
side for single-level occupancy, the Pauli potential derivative VP0 (r) being derived
by March and Nagy,28 for spherically symmetric ground-state densities n(r) and
for arbitrary level occupancy.

3.7.2. Example of harmonic confinement


As an explicit example of Eq. (3.45), let us utilize the differential equation for the
ground-state Fermion density ρ(r) given by Howard et al.23 in D dimensions, as
  
~2 ∂ 2 D+1 D ∂V
∇ ρ+ m+ ~ω − V (r) ρ0 (r) + ρ(r) = 0, (3.46)
8m ∂r 2 2 ∂r
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for m + 1 closed shells. Here, the confining potential energy has the harmonic form
V (r) = 12 mωr2 . Then it follows for D = 3 that VP0 (r) for that example is given by
March32 as
 
0 ~2 ∂ 2 2 ρ0 (r) 4 tvW 1 ∂tvW
VP (r) = ∇ ρ(r) + [(m + 2)~ω − V (r)] − +
3mρ(r) ∂r 3 ρ(r) ρ(r) r 2 ∂r
(3.47)
It is a straightforward matter to confirm this Eq. (3.47) for m = 0 corresponding to
single-shell occupancy (for which VP0 (r) = 0) by direct insertion of V (r) = 12 mω 2 r2 ,
and the corresponding density n(r) = n(0) exp(−βr2 ), where β = mω/~.

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As noted in March,32 it is relevant here to mention that Elliott et al.,33 in the


course of work on the semiclassical origins of density functionals, conclude, and we
quote them, ‘how much simpler the kinetic energy is as a functional of the potential
than of the density.’ While this is true in the ‘formally exact’ TF theory reported in
section 3.5.1, and especially Eq. (3.31), Eq. (3.32) makes the case for involving both
ρ and V in the expression for the kinetic energy density t(r). And this viewpoint is
supported by the one-dimensional result Eq. (3.15) of March and Young,9 which is
quite general.
Returning briefly to the Pauli potential VP (r), it was stressed especially by one
of us26,27 that VP (r) can be written formally exactly as

δTs [ρ] δTvW [ρ]


VP (r) = − . (3.48)
δρ(r) δρ(r)

Since TvW [ρ] is given quite generally by Eq. (3.2), the last term in Eq. (3.48) is
exactly known as an explicit functional of ρ(r). Thus VP (r) is equivalent to knowl-
edge of the functional derivative of the single-particle kinetic energy, which is the
focus of this review.

3.8. Non-local potential theory: V (r) 7→ V (r, r0 )

Very briefly, we will stress here first two points: (i) The Hohenberg-Kohn theo-
rem (applying to a local potential V (r)) can be generalized to non-local potentials
V (r, r0 ) considered by Bethe,34 motivated by Brueckner’s work; (ii) For the two-
level Fermion problem, one can construct the Dirac density matrix explicitly for
both V (r) and V (r, r0 ), using the density amplitude ρ1/2 (r) and phase θ(r)35

γ(r, r0 ) = ρ1/2 (r)ρ1/2 (r0 ) cos[θ(r) − θ(r0 )]. (3.49)

For local V (r), θ(r) is related to ρ(r) by the non-linear pendulum equation

∇ρ(r)
∇2 θ(r) + · ∇θ(r) + λ sin 2θ(r) = 0. (3.50)
ρ(r)

From Eq. (3.49), which holds for both local and non-local potentials, the single-
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particle kinetic energy density t(r) is given by

1 2
t(r) = tvW (r) + ρ (∇θ(r))
2
~2 (∇ρ)2 1 2
= + ρ (∇θ(r)) . (3.51)
8m ρ 2

But for non-local V , Eq. (3.50) has to be corrected by a Fock-operator–like piece.


So even for the same ρ(r), t(r) is different, as expected.

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3.8.1. Fine-tuning of Hartree-Fock (HF) density for spherical


atoms like neon

It is, of course, implicit that the exact ground-state density ρ(r) is needed to obtain
the single-particle kinetic energy Ts . But currently, this is not possible by DFT,
as we do not know the exchange-correlation contribution Vxc (r) to the required
one-body potential V (r).
Therefore, Cordero, March, and Alonso (CMA,36 ) have formulated a procedure
whereby, for light spherical atoms, fine-tuning of the HF-ground-state electron den-
sity can be achieved, which leads to ground-state densities for Be, Ne, Mg, and Ar
matching quantum Monte Carlo (QMC) densities in quality.
The motivation for the CMA study was the celebrated theoretical study of Møller
and Plesset37 who added Coulomb correlation effects to the HF approximation per-
turbatively. They emphasized the accuracy of the HF ground-state density ρ(r)
in atomic physics by demonstrating that this quantity was correct to second or-
der in the difference between the correct nonrelativistic Hamiltonian and the Fock
operator.
The idea underlying the CMA study was to start out from an unconventional
use of the HF method with nonintegral nuclear charge — say Z 0 — in order to (a)
insert semiempirically the correct nonrelativistic ionization potential, and (b) scale
the resulting density to satisfy Kato’s cusp condition38 for the electron density at
the atomic nucleus.
CMA then note, in the above context, that the numerically calculated HF density
(i.e. avoiding basis sets entirely) for species with nuclear charge Z 0 and N electrons,
ρHF (Z 0 , N, r), has the exponential decay at large distances r from the nucleus of
the form

p
ρHF (Z 0 , N, r) ∼ exp(−2 2IK (Z 0 , N )r), (3.52)

in atomic units, IK (Z 0 , N ) being the appropriate Koopmans ionization potential.


This, in turn, is the one-electron HF eigenvalue associated with the highest occupied
atomic orbital (HOAO). In contrast to Eq. (3.52), the exact exponential decay of
the non-relativistic (NR) electron density ρNR (Z, N, r) is known to be39
U.S. or applicable copyright law.

p
ρNR (Z, N, r) ∼ exp(−2 2INR (Z, N )r), (3.53)

where INR (Z, N ) is now the NR ionization potential of the neutral atom with atomic
number Z under consideration (now with N = Z). CMA describe an available
method which allows INR to be found semiempirically. But since, for the light
atoms considered by CMA, the corrections to the measured I are negligible, we
refer the reader to the original work for further details.

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Table 3.1. Ionization potentials in a.u. and fitted parameters for the atoms studied. After
Ref. 36.

Atom Z IK (Z, N ) Iexpt (Z, N ) INR (Z, N ) Z0 λ = Z/Z 0 IK (Z 0 , N )

Ne 10 0.850410 0.792482 0.794464 9.9128 1.0088 0.780612


Ar 18 0.591017 0.579155 0.582173 17.9802 1.0011 0.580883
Be 4 0.309270 0.342603 0.344332 4.1270 0.96922 0.366550
Mg 12 0.253053 0.280994 0.280740 12.0960 0.99207 0.285245

3.8.2. Scaling approach to obtain a correlated density ρ(r) from


HF densities for Ne and Ar
If we scale the HF density ρHF (Z 0 , N, r) obtained numerically for neutral atoms
with N equal to the true integer ataomic number Z (Z = 10, for the neon atom)
by solving the HF equations with non-integral nuclear charge Z 0 , then CMA next
scale this density using the norm-conserving Ansatz

ρλ (Z 0 , N, r) = λ3 ρHF (Z 0 , N, λr), (3.54)

where λ is a positive parameter near to unity. Then the asymptotic behaviour of


the scaled density is evidently
p
ρλ (Z 0 , N, r) ∼ exp(−2 2IK (Z 0 , N )λr). (3.55)

If Eq. (3.55) is required to decay in its long-range form just as the exact non-
relativistic density, that is ρλ (Z 0 , N, r) ∼ ρNR (Z, N, r), one must impose the condi-
tion
p p
IK (Z 0 , N )λ = INR (Z, N ). (3.56)

Furthermore, to satisfy Kato’s nuclear cusp condition, CMA show that

Z 0 λ = Z. (3.57)

This result (3.57) shows that the two parameters of the CMA model are not inde-
pendent.
We show in Table 3.1 for Ne and Ar, and also for comparison two other light
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spherical atoms, Be and Mg, the values of Z 0 and λ, plus relevant information on
the ionization potentials introduced above. For Ne and Ar, Z 0 is slightly less than
Z in each case, whereas for Be and Mg, Z 0 > Z, by about 0.1.
CMA make an extensive comparison with r space moments of QMC ground-state
densities, their results testifying to the high quality of the fine-tuned HF densities
thereby obtained.
In subsequent work, Amovilli et al.40 have extended the diagonal density
ρ(r) proposed by CMA to an off-diagonal idempotent one-particle density matrix.
Amovilli et al.40 show that the orthonormal used in this construction are then

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to be found from the solution of generalized HF equations. These authors report


calculations on the Be isoelectronic series of atomic ions with Z from Li− to Ca16+ .

3.9. Summary and directions for future studies

Emphasis is placed here on the way the forerunner of the currently used form of
DFT, namely the Thomas-Fermi statistical method, can be generalized without re-
course to Slater-Kohn-Sham orbitals. Such a generalization is shown to involve use,
say in a one-dimensional problem of independent Fermions moving in a potential
V (r), of the March-Young result for t(r) obtained by quadrature from Eq. (3.15),
plus a differential equation allowing the ground-state density n(r) to be calculated
from a given V (r) without recourse to one-body Schrödinger equations. To date,
such a differential equation is only known for special forms of V (r): as for example
in the case of harmonic confinement given in Eq. (3.35).
As for future directions in one dimension, it was noted by March and Murray41
that the so-called Slater sum S(r, β), related to the ground-state electron density
n(r, E) by Laplace transform41
Z ∞
S(r, β) = β n(r, E)e−βE dE, (3.58)
0

satisfies a partial differential equation which is known exactly for an arbitrary one-
body potential V (r), as summarized by Howard and March.42 S(r, β) is quoted
analytically in this article for harmonic confinement, and allows the differential
Eq. (3.35) to be recovered (see also Ref. 43).
In three dimensions, we have, to date, the formally exact generalizations of the
Thomas-Fermi semiclassical method set out here in Eqs. (3.29) and (3.32). At the
time of writing, however, the summation in Eq. (3.32) has only been completed
for harmonic confinement, namely when V (r) = 21 kr2 . But for this case, with
Fermions occupying an arbitrary number of closed shells, the kinetic energy density
functional is known in D dimensions, and the forms is quoted in Eq. (3.40). For
the future, further studies of the total kinetic energy directly from the density may
be prompted by the ongoing numerical work of Howard and March44 prompted by
Eq. (3.40). The reduction in weight of the von Weizsäcker term except for D = 1
is stressed there.
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We also gave attention in Sec. 3.7 to the concept of the Pauli potential VP (r),
which in turn is related to the functional derivative of the single-particle kinetic
energy by Eq. (3.48), where the von Weizsäcker term, of course, is explicitly known
in terms of the Fermion density ρ(r). Stress is also placed on the relation of the
Pauli potential to the exact differential virial theorem via Eq. (3.45), derived in
Ref. 28. It will be of considerable interest for the future if another route can be
found which allows the constraint of spherical symmetric ground-state densities in
Eq. (3.45) to be relaxed, thereby allowing possible analytic progress on molecules
and clusters by means of ‘orbital-free’ DFT.

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A.1. Exact correlated kinetic energy related to Fermion density in


model two-electron atom with harmonic confinement and
arbitrary interparticle interaction

There has been considerable activity in a model two-electron atom with harmonic
confinement and different interparticle interactions u(r12 ). This goes back to Kest-
ner and Sinanoğlu45 for the so-called Hookean atom with u(r12 ) = e2 /r12 as in
helium itself, and to Moshinsky 46 for also harmonic u(r12 ). Subsequently, Crandall
et al.47 solved for the spatial ground-state wave function Ψ(r1 , r2 ) for the inverse
2
square interaction λ/r12 .
This model atom problem was subsequently solved by Holas, Howard and March
(HHM)48 for arbitrary interparticle interaction u(r12 ) in that both the ground-state
Fermion density ρ(r), and the first-order correlated density matrix γ(r, r0 ), the off-
diagonal generalization of ρ(r), were obtained in terms of known functions plus the
one-variable relative (R) motion wave function ΨR (r), which only required solution
of a one-body radial Schrödinger equation with an effective potential

Veff (r) = Vext (r) + u(r), (A.1)

where Vext (r) = 12 kr2 is the harmonic confinement contribution to Veff (r). Just
this same input information was shown by HHM48 to determine γ(r, r0 ) by purely
quadrature.

A.1.1. Correlated relative motion kinetic energy density, in terms


of relative motion wave function ΨR (r)
HHM48 also derived an exact expression for the total kinetic energy T for arbitrary
u(r12 ), in terms of the wave function ΨR (r). Their result had the physical interpre-
tation that it was the sum of two ‘von Weizsäcker-like’ contributions, one of these
coming from the centre-of-mass motion, calculable once-for-all as it depended only
on Vext (r) in Eq. (A.1), and the other involving the first derivative dΨR (r)/dr of
the above relative motion wave function. The HHM result had the final form
Z  2
3 ~2 dΨR (r)
T = ~ω0 + dr, (A.2)
4 2mR dr
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where ω02 = k/m, with m the electron mass, k being the harmonic confinement
introduced following Eq. (A.1). The relative motion mass mR entering Eq. (A.2) is
obtained in Ref. 48 and is simply m/2.
Subsequent work by March, Akbari and Rubio30,31 has pointed out that it is
helpful next to extract from the HHM Eq. (A.2) a relative-motion kinetic energy
density tR (r) defined by the positive-definite quantity
 2
~2 dΨR (r)
tR (r) = . (A.3)
2mR dr

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Taking the square root of this equation, one can evidently write
 1/2
dΨR (r) 2mR 1/2
=± tR (r), (A.4)
dr ~2
with physical solution
 1/2 Z ∞
2mR 1/2
ΨR (r) = tR (s) ds. (A.5)
~2 r

To achieve the desired result for the exact correlated kinetic energy T in Eq. (A.2),
we next insert the wave function ΨR (r) into the HHM relation for the ground-state
density ρ(r) for this model with arbitrary interaction u(r12 ), namely
 2Z ∞  
8 r 1 2 sinh(ry/ac )
ρ(r) = √ exp − 2 dy y exp − y Ψ2R (ac y)
2
, (A.6)
π ac 0 4 (ry/ac )
ac being the length associated with the centre-of-mass Gaussian wave function
exp(−R2 /2a2c ), where
 1/2
~
ac = . (A.7)
2mω0

A.1.2. Some specific results for correlated kinetic energy of model


two-electron ground states
Evidently, by inserting Eq. (A.5) into Eq. (A.6), we find a functional relation be-
tween density ρ(r) and relative-motion kinetic energy density tR (r) of the form
ρ(r) = ρ [r; [tR ]] . (A.8)
Though, at the time of writing, no general proof has been given that a unique
inversion of Eq. (A.8) formally exists, we anticipate on physical grounds that this
will indeed be the case. Therefore we turn immediately to give results bearing on
Eq. (A.8), as discussed by March et al.30,31

A.1.2.1. The Hookean atom with Vext = 18 r2 and u(r12 ) = e2 /r12


Of course, the long term aim is to generalize the model of this Appendix to apply
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to the important problem of the ground state of the helium atom itself.
Then it is natural to take as the prime example of Eqs. (A.8) and (A.5) the
Coulomb interparticle repulsion u(r12 ) as
u(r12 ) = e2 /r12 . (A.9)
From the study of Kais et al.,49 ΨR (r) is known to take the form, for the specific
force constant k = 14 ,
2
 r
ΨR (r) = AR e−r /8 1 + , (A.10)
2

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0.006

0.005

0.004
tR (r)

0.003

0.002

0.001

0
0 1 2 3 4 5 6
r

Fig. A.1. Relative kinetic energy density tR (r) for the Hookean atom model, Eq. (A.12), in units
where 2mR /~2 = 1. Redrawn from Ref. 30.

where the normalization factor AR is given by


Z ∞
Ψ2R (r)4πr2 dr = 1. (A.11)
0

From Eqs. (A.10) and (A.3) it follows readily that, for this Hookean atom example
 h  2
2mR 1 −r 2 /4 r i
tR (r) = AR e 1−r 1+ (A.12)
~2 2 2
and a plot of tR (r) is shown in Fig. A.1 which is redrawn from the study of March
et al.30,31 The Fourier transform of the density ρ(r) entering the functional relation
Eq. (A.8) is known in particular cases, as discussed in Ref. 30.
For this case, ω02 = 14 with m = 1 in atomic units, and Eq. (A.2) for the exact
correlated kinetic energy T becomes (with ~ = 1, ω0 = 12 ),
3
T = + TR . (A.13)
8
U.S. or applicable copyright law.

The known value T = 0.664 au (readily calculated from the known wave func-
tion) yields from Eq. (A.13) that TR = 0.289 au.R As Kais et al. calculate,49
the von Weizsäcker inhomogeneity kinetic energy 18 ρ02 /ρ dr using ρ(r) in Ref. 30
gives TvW = 0.632 au and hence the ‘correlation’ kinetic energy defined here by
T − TvW = 0.032 au. This is more than 10% of TR entering the exact total kinetic
energy Eq. (A.13), the first term on the right-hand side being independent of the
interaction u(r12 ). To date, we have not found a way of writing TR in terms of ρ(r)
in as given in Ref. 30 for the Hookean atom.

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A.2. Transcending the von Weizsäcker single-particle kinetic


energy in an artificial two-electron atom

Recent work by Gál and March50 has been concerned with the energy density func-
tional of a specific artifical two-electron atom. This has again, as in section 3.6,
harmonic confinement with external potentia l 12 kr2 , but the electron-electron in-
teraction e2 /r12 , with r12 the separation of the two electrons, is replaced by the
inverse square law repulsion u(r12 ) given by
λ
u(r12 ) = 2 . (A.14)
r12

Gál and March50 construct the ground-state energy functional


Z
E[ρ] = F [ρ] + ρ(r)Vext (r)dr, (A.15)

by displaying F [ρ] as a quite explicit functional of ρ and the interaction strength λ,


but independent of Vext (r) = 12 kr2 .
This situation draws on the study of Capuzzi et al.,51 in which a differential
equation was derived for the groud-state density ρ(r) in the above model. This
equation reads
   
~ ~ 3 3 mω 2
rρ00 (r) + + r2 ρ0 (r) + r −α+2 r ρ(r) = 0, (A.16)
4mω 2mω 2 2 ~

where α = 21 [(1 + 4λm/~2 )1/2 − 1] is a measure of the repulsive coupling. Eq. (A.16)
has a solution in terms of hypergeometric functions.
The second important point is that the ground-state wave function ΨCWB (r1 , r2 )
and the corresponding energy FCWB are known in exact analytical form from the
work of Crandall, Whitnell, and Bettega (CWB).47 Utilizing these explicit results,
Gál and March50 find the form FCWB [ρ] for this model, as in Eq. (A.15), to be
Z  02 
~2 ρ (r) ρ0 (r)ρ00 (r)
+r dr
16m ρ(r) ρ(r)
FCWB [ρ] = Z   . (A.17)
1 ρ02 (r)
1− r2 − ρ(r) dr
3α + 8 ρ(r)
U.S. or applicable copyright law.

Taking the limit λ = 0, also corresponding to α = 0, Eq. (A.17) must reduce


to the single-particle von Weizsäcker form TvW [ρ], Eq. (3.2). This can be verified
explicitly using the well-known Gaussian density

ρ(r) = ρ(0) exp(−βr2 ), (A.18)

where β = mω/~, inserted into Eq. (A.17) in the limit α → 0.


The exact analytic result Eq. (A.17) means that for this, admittedly simplistic,
two-electron spin-compensated model, one of a very few forms of the functional F [ρ]
in the general DFT Eq. (A.15) is now available through Eq. (A.17) given in Ref. 50.

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References

1. P. Gombás, Die statistische Theorie des Atoms und ein anwendungen. (Springer-
Verlag, Vienna, 1949).
2. N. H. March, Adv. Phys. 6, 1 (1957).
3. N. H. March, Self-Consistent Fields in Atoms. (Pergamon Press, Oxford, 1975).
4. M. P. Tosi. Many-body effects in jellium., In ed. N. H. March, Electron correlation in
the solid state, chapter 1. (Imperial College Press, London, 1999).
5. C. F. von Weizsäcker, Z. Phys. 96, 431 (1935).
6. R. G. Parr and W. Yang, Density Functional Theory of Atoms and Molecules. (Oxford
University Press, Oxford, 1989).
7. J. C. Slater, Phys. Rev. 81, 385 (1951).
8. W. Kohn and L. J. Sham, Phys. Rev. 140, A1133 (1965).
9. N. H. March and W. H. Young, Nucl. Phys. 12, 237, (1959). Reprinted in Ref. 52.
10. P. A. M. Dirac, Proc. Camb. Phil. Soc. 26, 376 (1930).
11. N. H. March and A. M. Murray, Proc. Roy. Soc. A. 261, 119 (1961). Reprinted in
Ref. 52. See also Ref. 53.
12. J. C. Stoddart and N. H. March, Proc. Roy. Soc. A 299, 279 (1967). Reprinted in
Ref. 52.
13. W. J. Swiatecki, Proc. Phys. Soc. (London) A 63, 1208 (1950).
14. L. Wilets, Rev. Mod. Phys. 30, 542 (1958).
15. R. A. Berg and L. Wilets, Phys. Rev. 101, 201 (1956).
16. R. A. Berg and L. Wilets, Proc. Phys. Soc. (London) A 68, 229 (1958).
17. R. C. Brown and N. H. March, J. Phys. C 6, L363 (1973).
18. R. C. Brown and N. H. March, Phys. Rep. 24, 77 (1976).
19. N. H. March, W. H. Young, and S. Sampanthar, The Many-Body Problem in Quantum
Mechanics. (Dover, New York, 1995).
20. B. DeMarco and D. S. Jin, Science 285, 1703 (1999).
21. G. P. Lawes and N. H. March, J. Chem. Phys. 71, 1007 (1979). Reprinted in Ref. 52.
22. N. H. March, P. Senet, and V. E. Van Doren, Phys. Lett. A 270, 88 (2000).
23. I. A. Howard, N. H. March, and L. M. Nieto, Phys. Rev. A 66, 054501 (2002).
24. M. Levy and A. Görling, Phil. Mag. B 69, 763 (1994).
25. C. Herring and M. Chopra, Phys. Rev. A 37, 31 (1988).
26. N. H. March, Phys. Lett. A 113, 66 (1985). Reprinted in Ref. 52.
27. N. H. March, Phys. Lett. A 113, 476 (1986). Reprinted in Ref. 52.
28. N. H. March and Á. Nagy, Phys. Rev. A 78, 044501 (2008).
29. A. Holas and N. H. March, Phys. Rev. A 51, 2040 (1995). Reprinted in Ref. 52.
30. A. Akbari, N. H. March, and A. Rubio, Phys. Rev. A 76, 032510 (2007).
31. A. Akbari, N. H. March, and A. Rubio. Exact density matrix theory for the ground
state of spin-compensated harmonically confined two-electron model atoms with general
U.S. or applicable copyright law.

interparticle repulsion, to be published (2009).


32. N. H. March, Phys. Lett. A 372, 6667 (2008).
33. P. Elliott, D. Lee, A. Cangi, and K. Burke, Phys. Rev. Lett. 100, 256406 (2008).
34. H. A. Bethe, Phys. Rev. 103, 1353 (1956).
35. K. A. Dawson and N. H. March, J. Chem. Phys. 81, 5850 (1984). Reprinted in Ref. 52.
36. N. A. Cordero, N. H. March, and J. A. Alonso, Phys. Rev. A 75, 052502 (2007).
37. C. Møller and M. S. Plesset, Phys. Rev. 46, 618 (1934).
38. T. Kato, Commun. Pure Appl. Math. 10, 151 (1957).
39. T. Hoffmann-Ostenhof, M. Hoffmann-Ostenhof, and R. Ahlrichs, Phys. Rev. A 18,
328 (1978).

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40. C. Amovilli, N. H. March, and J. D. Talman, Phys. Rev. A 77, 032503 (2008).
41. N. H. March and A. M. Murray, Phys. Rev. 120, 830 (1960). Reprinted in Ref. 52.
42. I. A. Howard and N. H. March, phys. stat. sol. (b). 237, 265, (2003). Reprinted in
Ref. 52.
43. N. H. March and L. M. Nieto, Phys. Lett. A 373, 1691 (2009).
44. I. A. Howard and N. H. March, in the course of publication (2009).
45. N. R. Kestner and O. Sinanoğlu, Phys. Rev. 128, 2687 (1962).
46. M. Moshinsky, Am. J. Phys. 36, 52 (1952).
47. R. Crandall, R. Whitnell, and R. Bettega, Am. J. Phys. 52, 438 (1984).
48. A. Holas, I. A. Howard, and N. H. March, Phys. Lett. A 310, 451 (2003).
49. S. Kais, D. R. Herschbach, and R. D. Levine, J. Chem. Phys. 91, 7791 (1989).
50. T. Gál and N. H. March, J. Phys. B: At. Mol. Opt. Phys. 42, 025001 (2009).
51. P. Capuzzi, N. H. March, and M. P. Tosi, J. Phys. A 38, L439 (2005).
52. N. H. March and G. G. N. Angilella, Eds., Many-body Theory of Molecules, Clusters,
and Condensed Phases. (World Scientific, Singapore, 2009).
53. N. H. March and A. M. Murray, Proc. Roy. Soc. A 256, 400 (1960). Reprinted in
Ref. 52.
U.S. or applicable copyright law.

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Chapter 4

An Orbital Free ab initio Method: Applications to Liquid Metals


and Clusters

Andrés Aguado1 , David J. González1 , Luis E. González1 , Jose M. López1 ,


Sara Núñez1 and Malcolm J. Stott2
1
Departamento de Fı́sica Teórica, Universidad de Valladolid
47011 Valladolid, SPAIN
2
Department of Physics, Queen’s University
Kingston, ON K7L 3N6, CANADA

An orbital free ab initio scheme for the simulation of materials is described and
applications of the scheme to liquid metal systems, the solid-liquid metal inter-
face and to clusters are presented. The scheme is based on density functional
theory and first principles pseudopotentials. The electron system is described
entirely in terms of the electron density - it is free of orbitals - and the main
approximation is the use of an explicit but approximate density functional for
the electron kinetic energy. In addition, the absence of electron orbitals means
that the pseudopotential must be local. The scheme is compared and contrasted
with the popular Kohn-Sham approach in which the kinetic energy is treated
exactly and accurate first principles non-local pseudopotentials are used but, at
great computational cost. The error in the calculated total energy is found to be
acceptable for a class of systems which includes so-called simple metals and their
alloys but is not restricted to these e.g. good results have been obtained for Si
and Ga. For these systems the orbital free scheme allows the simulations of much
larger systems than can be treated with the full Kohn-Sham approach and long
molecular dynamics runs can be achieved. The scheme is useful for investigating
the static and dynamic properties of liquid systems and clusters.

Contents
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
U.S. or applicable copyright law.

4.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.2.1 Kohn-Sham approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.2.2 Orbital free approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.2.3 Pseudopotentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.2.4 Future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.3 OF-AIMD simulation of liquid metal systems . . . . . . . . . . . . . . . . . . . . . . . 71
4.3.1 Bulk liquid simple metals and alloys . . . . . . . . . . . . . . . . . . . . . . . . 72
4.3.2 Liquid Mg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.3.3 Liquid Ga . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.3.4 Liquid Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.3.5 Liquid Ga-In . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

55

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4.4 OF-AIMD studies of the liquid–vapor interface in simple liquid metallic systems . . . 90
4.4.1 Liquid Ga . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4.4.2 Liquid In . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.4.3 Liquid Ga-In . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.5 OF-AIMD studies of solid-liquid interfaces . . . . . . . . . . . . . . . . . . . . . . . . . 99
4.5.1 Surface relaxation and its temperature variation. Al(110) and Mg(101̄0) . . . . 100
4.5.2 Liquid Al on pinned solid Al . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.5.3 Liquid Li on solid Ca . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.6 OF-AIMD study of the melting-like transition in alkali clusters . . . . . . . . . . . . . 112
4.6.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.6.2 Analysis of the molecular dynamics . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.6.3 OF-AIMD simulations of melting in Na clusters . . . . . . . . . . . . . . . . . . 115
4.7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Appendix A. The kinetic energy functional . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
Appendix B. Position-dependent chemical potential . . . . . . . . . . . . . . . . . . . . . . 138
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

4.1. Introduction

The study of the structural and dynamical properties of disordered systems such as
liquids or clusters of atoms is greatly facilitated by the results of molecular dynamics
(MD) simulations in which the arrangement and velocities of the atoms consistent
with a given thermodynamical state and an assumed interatomic force law are
followed in time. Unlike crystalline systems in which periodicity and the harmonic
approximation form a good basis for studying the motion of the ions, liquids and
clusters are generally disordered at the atomic level and the motion of the ions is
complex. Inevitably, measured quantities for these systems involve an average over
configurations and these can be constructed from the results of MD simulations,
but in addition the simulations yield several dynamical magnitudes which are not
accessible to experiment and which provide knowledge of the microscopic atomic
arrangement and the way this evolves in time.
The study of the static and dynamic properties of liquid metals has already pro-
duced much experimental and theoretical work.1–6 The experimental investigation
of the structure and dynamical properties of liquid metals has mostly resorted to
radiation diffraction and inelastic scattering techniques, respectively. Both X-ray
diffraction (XD) and neutron diffraction (ND) have routinely been used in the de-
termination of the average atomic arrangement, as described by the static structure
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factor, S(q). Information on the atomic dynamics is contained in the dynamic


structure factor, S(q, ω), which can also be measured for which the main experi-
mental technique has been inelastic neutron scattering (INS); however, the recent
development of synchroton radiation facilities has enabled the possibility of using
inelastic X-ray scattering (IXS) as well. Other bulk properties such as the com-
pressibility, and the viscosity and diffusion coefficients can also be measured. On
the theoretical side, the development of microscopic theories such as the memory
function formalism or the kinetic theory, along with the realization that the decay
of several time-dependent properties can be explained by the interplay of two differ-

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ent dynamical processes, has created a theoretical framework whose application to


simple liquids has led to good qualitative results for several dynamical quantities.1–8
Small clusters of N atoms in the range N=10 or less up to a few hundreds are
of technological interest because they hold the possibility of being components in
the design of composite materials with special properties. But, they are of intrinsic
interest because of what we can learn from them of the factors influencing the
stability of atomic structures. Clusters of different sizes give systems with a range
of surface to volume ratios and the role played by the larger proportion of surface
atoms in the stability is of interest. The finite size of a cluster will lead to new
quantum mechanical effects in the electronic structure as energy gaps appear in the
electron energy spectrum. These factors influence the relative stability of clusters
of different size.9,10 the abundance population in cluster beams of alkali metal
atoms obtained by gas aggregation shows a spectrum with sharp peaks at some
particular sizes N=2,8,20,40,.... followed by sharp drops in the population. The
appearance of these so-called magic clusters was recognised as a consequence of an
electronic shell structure in which the magic sizes have filled electronic shells. In
addition to the influence of electronic shell closing on the cluster stability there
are also geometrical effects with clusters with complete icosahedral shells of atoms
being especially stable. The dynamics of the atoms in clusters manifests itself in
the melting of the clusters. Calorimetry and photofragmentation experiments have
yielded information on the way melting takes place and the size dependence of the
melting temperature, Tm (N) which exhibits a pattern of maxima and minima that
are not fully understood in terms of the electronic shells and atomic geometry.11–14
MD simulations have provided valuable insights into the dynamical effects which
lead to the melting of clusters.
Except for the lightest atoms the motion of the ions in MD is governed by
Newtonian mechanics.15 A sample set of ions representing a liquid are placed in a
cell and periodic boundary conditions are applied. The system is allowed to evolve
in time at chosen thermodynamic conditions under the action of the forces acting
on the ions. After sufficient time has elapsed for equilibrium to be established the
positions and velocities of the ions are recorded at each time and used to compute
average quantities of interest. Individual atomic configurations can be studied to
trace the origin of particular features. The representation of the liquid by the
simulation is limited by the number of atoms in the sample, which should be as
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large as possible to reduce the effects of the periodic boundary conditions, and by
the time over which configurations are available for the calculation of dynamical
quantities, which should be as long as possible. The size of the sample cell and the
simulation time place lower limits respectively on the wave vectors and frequencies
of phenomena relevant to the liquid. The simulation of a cluster often also applies
periodic boundary conditions because of technical reasons related to the treatment
of the electrons. If this is the case the cell containing the cluster must be sufficiently
large to accommodate the cluster and enough vacuum to minimize the interaction

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between a cluster and its neighbouring images in the superlattice. The study of
cluster melting also requires long simulation times so that the system samples the
many isomeric possibilities. Dealing with these factors of the size of the sample and
simulation time depend on the computing resources available and the patience of the
practitioners. These issues aside, the accuracy with which the simulation represents
the particular liquid system or cluster depends on the assumed interatomic forces.
Early MD simulations were entirely classical using model potentials such as hard
sphere or Lennard-Jones potentials. These classical MD studies gave useful insights
into generic liquid and cluster behaviour. However, a simulation with the objective
of investigating a particular system requires forces appropriate to the system. The
valence electrons play a crucial role in the behaviour of metallic systems, forming a
glue that holds together the ions against the Coulomb repulsion of the ionic charges.
The embedded atom model (EAM) of Daw and Baskes16 incorporates the electron
density in the interaction energy following the work of Stott and Zaremba17 and has
been used successfully for metallic systems. However, the interaction is empirical
and results can depend substantially on the way the parameters are chosen. In prin-
ciple, the solution of the Schrodinger equation for the electrons provides the energy
of the system and from this the forces on the ions, but there are many electrons to
be considered and these are coupled one to another by their Coulomb repulsion as
well as to the ions. The complexity posed by the electron-electron interactions can
be handled by Density Functional Theory (DFT)18,19 which introduces the electron
density distribution as a fundamental variable for the system, and shows how to
replace the interacting many-body system of electrons by an auxiliary system of non-
interacting particles moving in an external field, a much simpler system amenable
to solution. DFT is the basis of present-day simulations. Pseudopotentials are the
second important ingredient for the calculation of the forces on the ions including
a treatment of the electrons.20 It is the valence electrons that respond to the ar-
rangement of the ions and contribute to the forces on them. Many of the electrons,
the so-called core electrons, are tightly bound in the ions and move with them, are
insensitive to the surroundings and contribute negligibly to the forces. The core
electrons may be removed and their effect incorporated in a pseudopotential which
gives an accurate description of the valence electrons. The use of a pseudopoten-
tial has an additional practical benefit. The pseudowavefunctions that result are
much smoother than their all-electron Kohn-Sham orbital counterparts and may be
U.S. or applicable copyright law.

accurately represented by plane waves with great computational advantages. The


approach to simulations based on the two pillars of DFT and pseudopotentials has
become known as the ab initio method.
If the electron-ion interaction is sufficiently weak the electrons respond linearly
to the pseudopotential and the ions interact with one another through a pair po-
tential21 which can be used very efficiently in MD simulations.15 Such a scheme
was often used to investigate bulk liquid alkali and other simple metal systems.
Although some effect of the electrons is incorporated in this effective ion-ion inter-

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action it is assumed that the electron distribution is weakly perturbed by the ions
and the pair potential is rigid. This cannot be the case when there are substantial
variations in electron density such as occur at a liquid-vapor interface or at the
surface of a cluster where the electron density decays from its bulk value inside to
zero outside. Similar problems with this perturbative approach must also occur at
the interface between dissimilar metals and in many alloys. For example, in the ho-
movalent LiNa liquid alloy the valence electron density will almost double in going
from a Na rich to a Li rich region merely because of the atom size difference. A
realistic simulation of these situations requires forces on the ions that take account
of changes in the underlying electron density near them.
The most common application of DFT in simulations uses the approach of Kohn
and Sham19 (KS) who introduced the electron kinetic energy functional, Ts [n], for
an auxiliary system of independent particles with the same density n(~r) as the
physical electron system of interest. This step isolates all effects of the electron-
electron interaction in a single term, the exchange-correlation energy functional,
Exc [n], for which approximations have been developed that approach chemically
useful accuracy. KS then showed how to evaluate Ts [n] exactly in terms of the
single particle orbitals, φi (~r) for the auxiliary system which are self-consistent
solutions of the Schrodinger equation with an effective external potential for which
the prescription is given. This KS ab initio molecular dynamics (KS-AIMD) scheme
by-passes the functional Ts [n] but at the cost of moving away from the electron
density as the fundamental variable and working instead with a set of orbitals, one
per electron. The most successful pseudopotentials have been developed for use
in the KS-AIMD approach.22–24 They are fitted to the free atom, are transferable
to the atom in other environments of interest, for example a liquid metal, but are
nonlocal in the sense that different potentials act on different angular momentum
components of the KS orbitals.
The orbital free (OF) approach25–27 follows the KS development of DFT but re-
tains the electron density as the fundamental variable. Because the KS orbitals are
no longer needed, memory requirements scale linearly with system size as opposed
to quadratically for the KS approach. There are also enormous savings in computa-
tional time because there is only the density distribution to manipulate rather than
the whole set of orbitals, provided the Ts [n] is simple to evaluate. Costly orthogo-
nalization of the orbitals and Brillouin zone sampling are no longer required. The
U.S. or applicable copyright law.

savings in computational time and memory of the OF scheme allow for the simu-
lation of much larger systems for longer simulation times than would otherwise be
possible. However, an explicit form for Ts [n] as well as Exc [n] is required, and since
only approximate forms for Ts [n] are known errors are made in the kinetic energy
which can be serious because the kinetic energy is the same order of magnitude as
the total energy whereas Exc is typically only 10% of the total. Another consequence
of the freedom from orbitals is that the highly transferable nonlocal pseudopoten-
tials cannot be used and a local potential is needed for the electron-ion interaction.

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An approximate form for Ts [n] and a prescription for constructing a local pseu-
dopotential have been developed and applied in OF simulation studies of a variety
of liquid metal systems and of clusters. Because of the approximations involved
in Ts [n] the method is best suited to simple metal systems such as the alkalis,
alkali-earths, Al, In, Tl and their mixtures which do not exhibit directional bond-
ing, but applications to liquid Si which is weakly metallic and has some remnants
of the bonding present in the solid have been rather successful. The theoretical
foundation of the orbital free ab initio molecular dynamics (OF-AIMD) approach
is presented in Sec. 4.2 with particular emphasis on the method we have developed
and applied. Section 4.3 reviews applications of the method in simulations of bulk
liquid metals and alloys with emphasis on the dynamical properties for which the
method is well suited. The next section is devoted to applications of the OF-AIMD
method to investigate the interface between a solid and a liquid metal. Applications
to the dynamical properties of metal clusters follows in Sec. 4.6 where studies of
the melting-like transition in alkali clusters is described.

4.2. Theory

~ l}
The total energy of a system of N classical ions carrying charge Z at positions {R
in a volume V , and interacting with Ne = N Z valence electrons, may be written
within the Born-Oppenheimer approximation as
~ l }) = Tion + Vion−ion + Ee ({R
E({R ~ l }) (4.1)
where the first two terms are the ion kinetic energy and the direct Coulomb inter-
action energy, and Ee is the ground state energy of the electrons in the presence of
the ions. The force on an ion isa
X ∂Ee
F~i = Z 2 R~ij /Rij
3
− (4.2)
~i
∂R
j

where R~ij = R ~ i − R~j and the Hellman-Feynman theorem36 has been used. The
simulation then proceeds by solving Newton’s equations for the ions numerically
using, for example, the Verlet algorithm and a suitable time step ∆tion .15
Density functional theory18,19,28,29 shows that the electronic energy can be writ-
ten as a functional of the electron density, n(~r), as follows19
U.S. or applicable copyright law.

E[n(~r)] = Ts [n] + Eext [n] + EH [n] + Exc [n] (4.3)


where Ts [n] is the kinetic energy of a non-interacting system of density n(~r), Eext
is due to the interaction of the electrons with the ions, EH [n] is the classical elec-
trostatic Hartree energy given by
Z Z
1 n(~r) n(~s)
EH [n] = d~r d~s , (4.4)
2 |~r − ~s|
a Atomic units are used throughout, unless stated otherwise, with ~ = e = me = 1

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and Exc [n] is the exchange–correlation energy, for which well tested approximations
are available.
The exchange-correlation energy has been the subject of a great deal of re-
search30 because the only obstacles to an exact treatment of the electronic energy
using the KS-AIMD method described in the next section lie in this term. Ap-
proximate forms of Exc [n] are of two types. The first are local density approxi-
mations (LDA) in which the electron gas is treated locally at ~r as though it were
a uniform electron gas of mean density n(~r), and uses the results of many-body
calculations of the uniform interacting gas. Two popular LDA approximations31,32
are parametrizations of the results of Monte Carlo treatments of the interacting
electron gas of Ceperley33 and Ceperley and Alder.34 More sophisticated approx-
imations involve density gradients as well as the density at ~r and are known as
generalized gradient approximations (GGA); one in common use is due to Perdew
et al.35 However, the simple LDA is usually sufficient in OF calculations because
the errors associated with the approximate kinetic energy functional are expected
to be much greater than those associated with Exc [n]. Superlattice geometry is
usually adopted in which the N atoms of interest are located in a cell of volume V
and replicated so that the whole system consists of a periodic superlattice.36 If the
target of the simulation is a bulk crystalline system the supercell would consist of
one or more unit cells of the material. In the case of a liquid, superlattice geometry
would again be adopted with periodic boundary conditions applied as in the motion
of the ions, but to minimize the effects of the artificial periodicity the sample N of
atoms in the cell must be as large as possible. The simulation of an isolated cluster
of N atoms would position the atoms in a cell large enough so that the cluster is
surrounded by empty space and the interaction between a cluster and its periodic
images is negligible. Similarly, for a liquid–vapor interface a slab of liquid would be
positioned in a cell with empty space above and below so that interaction between
a slab and its neighboring images can be neglected. The superlattice geometry is
so often employed, even for systems which are patently not periodic, because Bloch
wave methods for solving the electronic structure can be used and, in particular,
the electronic structure can be represented by a discrete set of plane waves and
manipulated with the highly efficient fast Fourier transform algorithm.

4.2.1. Kohn-Sham approach


U.S. or applicable copyright law.

Kohn and Sham19 introduced the orbitals, φi (~r), of the system of independent
particles having the same density as the interacting system of interest and moving
in the effective field vef f . The orbitals satisfy the single particle equations
1
(− ∇2 + vef f [n, ~r])φi = i φi , i = 1, 2, . . . (4.5)
2
which must be solved self-consistently because the effective potential vef f depends
explicitly on the density, which is obtained from the occupied orbitals,

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X
n(~r) = |φi (~r)|2 (4.6)
occ

The ground state kinetic energy, Ts , can be obtained exactly in terms of these
orbitals
Z X  
1
Ts = d~r φi (~r)∗ − ∇2 φi (~r) (4.7)
occ
2

which leaves Exc [n] as the only small source of error in Eq. (4.3) for the electronic
energy of the ground state. In addition, highly accurate and transferable nonlocal
pseudopotentials may be used for the electron-ion interaction. In practice the KS
equations are not solved directly, a time consuming process, instead the ground
state electronic energy is found by minimizing iteratively the energy functional with
respect to the orbitals while ensuring that the orbitals are mutually orthogonal.36
Orthogonalization is itself time consuming requiring order N 3 operations. Storing
the order N orbitals and manipulating them place computational limits on the
number of atoms that can be simulated and the length of the MD run. The most
that can be done at present are about a few hundreds of atoms, which is a small
sample of a bulk liquid, and for a few tens of picoseconds, which is a time too
small to investigate dynamical effects. Similar limits also apply to the simulation
of clusters. These limits will no doubt be surpassed in the future as computer
technology advances, and strides are being made to develop DFT based procedures
that scale as order N , but at present the OF-AIMD approach is the only choice for
realistic simulations of liquid metals and large clusters.

4.2.2. Orbital free approach

If an explicit density functional is adopted for Ts [n], the ground state energy can
be obtained byR minimizing E[n] in Eq. (4.3) with respect to the density subject to
the constraint d~r n(~r) = Ne which maintains the number of electrons as Ne . The
choice of Ts [n] will be discussed later. Minimization could proceed by expanding
n(~r) in a set of plane waves having the periodicity of the superlattice, as follows
X ~
−iG·~
r
n(~r) = nG
~ e (4.8)
U.S. or applicable copyright law.

~
G

~ = 2π (n1 , n2 , n3 ) .
G (4.9)
L
where L is the side of the supercell assumed for simplicity to be a cube, and min-
imizing E[n] with respect to the nG ~ . The number of electrons can easily be held
constant by keeping nG=0 ~ = Ne /V . However, it is necessary physically to maintain
n(~r) ≥ 0 – if this is breached the iterative minimization becomes unstable – and
this constraint is difficult to impose with this approach.

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Instead of using n(~r) as the system variable, we have had success using a single
effective orbital ψ(~r) where n(~r) = ψ(~r)2 . If ψ(~r) is initially real it stays real
throughout the iterations and n(~r) is guaranteed non-negative. Representing ψ(~r)
in the plane waves
X ~
−iG·~
r
ψ(~r) = cG
~ e (4.10)
~
G

minimization can be performed with respect to the Fourier coefficients, cG ~ . The


plane wave expansion is truncated at a maximum wave vector Gc corresponding to
an energy cutoff Ec = G2c /2. Plane waves are a good basis set for the systems we
have treated; they span the whole space, they are independent of the ion positions,
and the completeness is controlled by the single parameter Ec which can be var-
ied to test convergence. In contrast, constraining the number of electrons during
minimization is harder to accomplish with ψ(~r) than when working directly with
n(~r).
The ground state energy for Ne electrons can be obtained by treating the co-
efficients cG
~ as dynamical variables and conducting a simulated anneal as first
P
introduced by Car and Parrinello.37 A fictitious kinetic energy, |ċG 2
~ | /2Mc is
introduced and the equation of motion for the cG~ is

Z
~
~ = −2
Mc c̈G d~r µ(~r)ψ(~r)eiG·~r + 2µ̄V cG
~ (4.11)

where µ(~r) = δE/δn(~r) and µ̄ the chemical potential for which the system contains
the required number of particles Ne . These equations are solved numerically using
the Verlet leapfrog algorithm36,38 with an electronic timestep ∆tc . The velocities
ċG
~ are reduced at every timestep or so and the system cools until static equilibrium
– the electronic ground state – is reached to within preset tolerances. However,
the chemical potential
R µ̄ is not knownR in advance but replacing µ̄ in Eq. (4.11) by
its stationary value
R d~r µ(~
r )n(~
r )/ d~
r n(~r ) at each timestep, and renormalizing the
density so that d~r n(~r) = Ne , gives good convergence to the ground state.

4.2.2.1. The kinetic energy functional


U.S. or applicable copyright law.

The use of an explicit electron kinetic energy functional, Ts [n], is the main feature
distinguishing the OF from the full KS scheme. The theorems of Hohenberg and
Kohn show that such a functional exists but little is known about the form of the
functional, and compared to the exchange–correlation energy functional, Exc [n],
little work on Ts [n] has been done although the prospect of an accurate OF-AIMD
scheme has stimulated interest and several approximate functionals have been pro-
posed recently. Approximate forms have been based on the known forms of Ts [n]
in a few limiting cases.

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4.2.2.2. Known limiting cases


In the limit of a uniform noninteracting electron gas the kinetic energy is given by
the Thomas–Fermi (TF) functional39–43
Z
TTF = a0 d~r n(~r)5/3 (4.12)

where a0 = 3(3π)2/3 /10, and this functional is appropriate for systems in which
the electron density, n(~r) is slowly varying. Indeed, the TF functional is the lead-
ing term in an expansion of Ts [n] in density gradients. The gradient expansion was
first developed by Kirzhnits44 who reported the second and fourth order corrections
to the TF result. An error in the fourth order term was noted and corrected by
Hodges45 whose method is easy to follow. Subsequently, the sixth order term has
been obtained by Murphy.46 The calculation of these gradient corrections becomes
increasingly complicated with the order and although corrections higher than the
sixth can undoubtedly be calculated the effort may not be worthwhile. The func-
tional may be written
Z
Ts [n] = d~r ts (~r) (4.13)

in terms of a kinetic energy density, and gradient corrections up to fourth order are
t(0)
s = a0 n
5/3
(4.14)

|∇n|2
t(2)
s = (4.15)
72n
" 2   2  4 #
n1/3 ∇2 n 9 ∇2 n ∇n 1 ∇n
t(4)
s = − + (4.16)
540(3π 2 )2/3 n 8 n n 3 n

A few points regarding the gradient expansion are worth noting. The fourth order
(4)
correction, ts , involves |∇n|2 and ∆n which are readily calculated, but not the
fourth derivative. It is also positive everywhere. For an exponentially decaying den-
sity such as one would find in the outer region of an atom or molecule, or outside
(6)
the surface of a solid or a liquid, ts and higher order terms diverge exponentially.
These results are for a three dimensional system, but curiously, for two dimensions
U.S. or applicable copyright law.

all density gradient corrections of the Kirzhnits type to the TF functional van-
ish.47,48 This is not to say that TF is exact in two dimensions but rather that there
are technical problems with the expansion.
The von Weizsäcker functional49
Z
1 |∇n|2
TvW = d~r (4.17)
8 n
p
is exact for a one electron system for which ψ(~r) = n(~r) (or for two if the state is
doubly occupied for spin) and is therefore correct in the outer regions of a localized

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system. It has the same form as the leading, second order, correction in the density
gradient expansion only a factor of 9 larger. In addition, TvW is widely held to be
correct in the limit of a rapidly varying density and this is supported by a result of
linear response (LR) theory to which we now turn.
A weakly perturbed uniform electron gas provides another limiting case for the
kinetic energy functional.50 If the gas has density n̄ and the LR of the system to the
perturbing potential leads to a change in density δn(~r), then perturbation theory
to second order in the potential gives for the kinetic energy
1X
TLR = V n̄5/3 + δñ~q [χ(q, n̄)]−1 δñ−~q (4.18)
2
q6=0
~

where
Z
δñ~q = d~rδn(~r) exp(i~q.~r) (4.19)

and χ(~
q ) is the so-called Lindhard function given by
 
k̄F 1 − x2 1+x
q) = − 2 1 +
χ(~ ln | | , x = q/2k̄F (4.20)
2π 2x 1−x
where k̄F is the Fermi wavevector R corresponding to the electron density n̄. The
(2)
second order gradient correction d~r ts (~r) (Eq. 4.15), and TvW (Eq. 4.17) have the
same form but differ by a factor 9. Jones and Young51 analysed the LR result for the
kinetic energy and showed that the factor 1/72 is correct when the dominant Fourier
components of the perturbing potential are at small wavevector ~q, that is when the
potential is slowly varying. However, when the dominant Fourier components are
at large ~
q and the potential is rapidly varying, the von Weizsäcker term with its
factor of 1/8 is correct.

4.2.2.3. Approximate functionals


Several approximate kinetic energy functionals have been proposed which give the
TF, von Weizsäcker and the LR results in the appropriate limiting conditions.
The first of these was due to Wang and Teter52 who also investigated the possi-
bility of including quadratic response. With Perrot’s work as the basis,53 Madden
and coworkers54,55 have developed functionals which also correctly recover the TF,
U.S. or applicable copyright law.

von Weizsäcker and LR limits54 and they too included the quadratic response.55
OF-AIMD simulations of simple metal systems using such functionals, have yielded
promising results. Later, Carter and coworkers56 investigated these functionals, and
proposed a linear combination of functionals as a suitable form for Ts . The evalua-
tion of these functionals requires only order N operations and OF-AIMD simulations
based on them are very efficient. Unfortunately, they have two undesirable features.
They are not positive definite, so that minimization of the energy functional can
lead to an unphysical negative kinetic energy. Secondly, the functionals that incor-
porate the weakly perturbed electron gas through the linear or higher order response

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functions must specify a reference uniform electron gas density, n̄. In the case of
systems such as bulk liquid simple metals in which there are small variations in the
electron density, the mean electron density of the system is an appropriate choice for
n̄. However, the choice of a uniform reference system is problematic when there are
more substantial variations in electron density such as may appear in some simple
metals and alloys, for example when the components of an alloy have a large size
and/or valence difference, and especially for the surface of a solid or a liquid where
the electron density drops through the interface from the bulk value to zero in the
vacuum.
Approximate functionals of the GGA form have been proposed which include
some features of electron gas LR but avoid the need for a uniform reference density.
The first of these due the DePristo and Kress57,58 incorporated the correct small ~q
and large ~q forms of the LR function and fitted parameters in a Pade approximant to
the total kinetic energy of all-electron Hartree-Fock rare gas atoms. Wang et al.59
investigated GGA’s more appropriate for smoother pseudodensities. Parameters
were fit to give δTs /δn(~r) = −V (~r) + µ for a model pseudoatom. The gradient
expansion through fourth order was found to give good kinetic energies and it was
suggested that an interpolation between the gradient expansion including fourth
order for slowly varying density and TvW when densities are rapidly varying might be
a useful kinetic energy functional. Perdew and Constantin60 developed a functional
that met these requirements and tested it for a variety of systems by evaluating
it for an exact density and comparing the results with the corresponding kinetic
energy. Their functional was reported to be typically a strong improvement over
the gradient expansion. However, to be useful in OF-AIMD simulations not only
Ts [n] but also δTs /δn(~r) must be accurate so that the variational principle can
be used to obtain the ground state density n0 (~r) and hence Ts = Ts [n0 ], and the
functional is untested in this regard. A functional of this type is attractive because
is does not require a uniform reference density and might be more widely applicable
than those that incorporate uniform electron gas response functions52–55 and are
limited to systems in which the variations in electron density about the mean value
are small. However, it cannot give any Fermi surface effects that would be expected
for metallic system such as Friedel oscillations. Even so, tests should be performed
for impurities in a gas and for the jellium surface to determine if some perhaps
truncated or damped oscillatory behaviour in the density is present.
U.S. or applicable copyright law.

Chacón, Alvarellos and Tarazona61 have developed a different type of kinetic


energy functional, which employs an “averaged density” and recovers the TF, von
Weizsäcker and LR limits.
The functional has been investigated and generalized by Garcı́a-González et
al.62–64 These functionals have the merit of incorporating Fermi surface effects
through the uniform gas response but do not require a fixed reference density, and
they can be chosen to be positive definite, an essential requirement if they are to
be used variationally. However, they are somewhat complicated to apply and more

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time consuming to evaluate because they require an additional level of computation


in order to determine the averaged density. Consequently, they scale as order N2
which diminishes the advantage of the OF-AIMD approach over the full KS-AIMD
method.
In most of the applications of the OF-AIMD scheme to be described later, the
simplified version of González et al.27,65 of the averaged density approach of Chacón,
Alvarellos and Tarazona61 and Garcı́a-González et al.62–64 has been used, with the
kinetic energy given by

Ts = TvW [n] + Tβ [n] (4.21)


Z
3
Tβ [n] = d~r n(~r)5/3−2β k̃(~r)2 (4.22)
10
Z
k̃(~r) = (2k̄F )3 d~s k(~s)wβ (2k̄F |~r − ~s|) (4.23)

k(~r) = (3π 2 )1/3 n(~r)β , (4.24)

where k̄F is the Fermi wavevector corresponding to a reference mean electron density
n̄, and wβ (x) is a rigid weighting function, determined by requiring the correct
recovery of the LR limit at the reference mean density and the T-F limit. The
advantage of the simplification is that k̃(~r) appears as a convolution which for a
plane wave basis can be performed rapidly by the usual fast Fourier transform
techniques. This renders the functional order N in scaling. The functional is a
generalization of one with β = 1/3, used earlier in a study of expanded liquid Cs.66
The details of the functional are given in González et al.27,65 and are reproduced
in appendix A. Its main characteristics are as follows: (i) β is a real positive
number whose maximum value still leading to a mathematically well behaved weight
function is ≈ 0.6, (ii) the functional recovers the uniform and LR limits, and is
positive definite (iii) when k̄F → 0 because the mean electron density vanishes, e.g.
for a finite system, the von Weizsäcker term is recovered if β = 4/9, whereas for other
values of β, the limit is TvW + CTTF , (iv) for values of β > 0.5 it is expected that
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µ(~r)ψ(~r), which is the driving force for the dynamic minimization of the energy,
remains finite even for very small electron densities n(~r). For systems in which
there will be regions where the density will decay exponentially such as clusters
or a liquid/vapor interface the von Weizsäcker term should appear limit of the
functional and a value of β as close as possible to 4/9 is called for. Unless otherwise
stated the simulations described later used β = 0.51, which in the limit n̄ → 0
gives C = 0.046 and guarantees, at least for the systems considered, that µ(~r)ψ(~r)
remains finite and not too large everywhere so that the energy minimization can be
achieved.

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4.2.3. Pseudopotentials
Ab-initio simulations using the KS-AIMD approach invariably employ nonlocal
pseudopotentials obtained by fitting to properties of the free atom.22,23 The non-
locality is a consequence of the pseudopotential acting on the pseudoatom stripped
of the core electrons - the pseudoion - having different potentials acting on different
angular momentum components of the valence electron orbitals.
lmax
X
Vion = vlocal (~r) + |l, m > δvl (r) < l, m| (4.25)
l,m

where lmax is usually 1 or 2. The nonlocal part of the potential is time consuming
to evaluate with a plane wave basis and in ab initio simulations a procedure due to
Kleinman and Bylander67 is invariably used which leads to a factorization of the
matrix elements and considerable time saving.
The fitting procedure of the so-called “norm conserving” pseudopotentials guar-
antees that the pseudoion scatters electrons in the same way as the true ion not
only at the valence energy levels but also over an energy range about them. These
pseudopotentials work well for many elements, but for some e.g. oxygen and the
3d transition elements, the ion core is small, and extensive and therefore costly
plane wave basis sets are necessary. For these and other cases Vanderbilt’s ultrasoft
pseudopotential24 is often used. Vanderbilt enlarged the ion core leading to a softer
pseudopotential, but at the cost of sacrificing the norm conservation which required
some adjustment to the charge density.
Since the OF scheme is free of orbitals the ion-electron interaction energy has
the form
Z
Ee−ion = d~r V (~r)n(~r) (4.26)

where n(~r) is the electron pseudodensity,


X
V (~r) = ~ i)
vi (~r − R (4.27)
i

and vi (~r) is the electron-ion interaction for ion i. This form would seem to exclude
the possibility of using nonlocal pseudopotentials like eq. (4.25) in OF-AIMD sim-
ulations and a local pseudopotential must be selected. But, this question is worth
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further study.

4.2.3.1. Local pseudopotentials


There are two types of local pseudopotentials. Most are empirical and often have
some simple analytic form; a few are from first principles. Early OF calcula-
tions25,54,55,66,68 used empirical local pseudopotentials. However, great care must
be taken in using empirical potentials outside the set of data used in their fitting
and the degree of confidence to be placed in the results is unknown. A successful

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application of an empirical pseudopotential in an OF scheme is the work of Aguado


and López in their studies of the melting of small metal clusters.69–72 The two pa-
rameter analytic local ion pseudopotential of Fiolhais et al.73,74 was assumed and
the parameters were chosen so that the OF-AIMD results reproduced KS-AIMD
results for the interatomic forces and relative energies of a few selected cluster
configurations. For a wide size range of Na clusters average forces and energy dif-
ferences were reproduced very well. The potentials thus fitted and used within the
OF-AIMD scheme led to an explanation of the anomalous size dependence of the
melting temperatures of Na clusters. This and related applications of the OF-AIMD
scheme to metal clusters is the subject of Sec. 4.6.
Ideally, a local pseudopotential would be used for the electron-ion interaction
which is fitted to give the suitably pseudized free atom electron density and de-
signed to be transferable from the atom in free space to the atom in other electronic
environments of interest. Wang and Stott obtained first principles local pseudopo-
tentials for group IV elements based on the free atoms.75 The electron density of
the free pseudoatom used to construct the nonlocal pseudopotential in, for instance,
the Bachelet-Hamman-Schluter22 or the Troullier-Martins23 schemes can of course
be constructed from the nonlocal potential, but DFT tells us that there is a unique
local pseudopotential that yields the same density. The potentials constructed in
this way may be regarded as the local equivalents of the nonlocal pseudopotentials.
Wang and Stott found such local potentials for C, Si and Ge and used them in full
KS calculations of dimers and crystalline solids. Fairly good results were obtained
for bond lengths and lattice constants while the results for energies compared less
well with the results obtained using the original nonlocal potentials.
In the absence of a transferable local pseudopotential based on the free atom, an
alternative is to base the pseudopotential on a reference system in which the envi-
ronment of the atom is similar to that for the physical systems of interest. Watson
et al.76 used a bulk crystal as a reference system. KS calculations were performed
for a popular nonlocal pseudopotential and the Fourier components of the electron
density were obtained. The Fourier components of the local KS effective potential
which produced this density using the OF functional were found and “unscreened”
to yield the local ion pseudopotential. Some interpolation was necessary in order to
obtain the potential at all q-values, not just those at the reciprocal lattice vectors
of the reference crystal. Application of these pseudopotentials using the OF scheme
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gave good agreement for a variety of crystalline properties with the results of full
KS calculations with the original nonlocal pseudopotential for Na, Li and Al.
Applications of the OF-AIMD method to liquid metal systems presented in
Sec. 4.3 use a first principles local pseudopotential similarly constructed from the
electron density obtained from a full KS calculation treatment of a liquid-like ref-
erence system.27 The reference system has the atom at the centre of a spherical
cavity in the positive background of a uniform electron gas having density equal
to the mean valence electron density of the system of interest. The radius of the

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cavity is such that the positive charge removed to make the hole is equal to the
valence charge of the atom, and a so-called neutral pseudoatom77,78 is formed. This
reference system represents the situation of an atom in a liquid metal when its sur-
roundings are smeared out to form a uniform gas. The first step in the construction
is an all-electron KS density functional calculation to obtain the displaced valence
electron density, nat (r), i.e. the change in the electron density induced by the atom
and the cavity. Next, nat (r) is pseudized by removing the contribution from core
electrons and eliminating the core-orthogonality oscillations to give nps (r). Finally,
an effective local ion pseudopotential is found using the OF density functional which,
when inserted into the uniform electron gas along with the cavity, reproduces the
pseudized displaced electron density. The development proceeds as follows. The
minimization of the energy functional gives the Euler-Lagrange equation for the
pseudopotential in the jellium-vacancy system:
µs (r) + Vext (r) + VH (r) + Vxc (r) − µ = 0 , (4.28)
where each of the terms is the derivative of the corresponding term in Eq. (4.3),
namely,
µs (r) = µvW (r) + µβ (r) , (4.29)
with the expressions for the von-Weizsäcker term and the β-term given in appendix
B,
Vext (r) = vps (r) + vcav (r) + vjell (r) , (4.30)
Z
VH (r) = d~sn(s)/|~r − ~s| , (4.31)

with n(r) = n̄ + nps (r). Given n(r), vps (r) can be obtained from Eq. (4.28), and
the constant µ is an energy origin set to give a pseudopotential that decays to zero
at large distances.

4.2.4. Future prospects


The OF-AIMD scheme based on this neutral pseudo-atom pseudopotential and the
order-N averaged density electron kinetic energy functional, Eq. (4.22), gives a good
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account of static and dynamic properties of several liquid simple metals and alloys
including the alkalis, alkali-earths, Al, In, Tl and some systems that would not
normally be regarded as simple, such as Si and Ga. However, a significant unsatis-
factory feature of this scheme is the dependence of both the kinetic energy functional
and the pseudopotential that is adopted on some uniform electron gas reference sys-
tem. For example, in their OF-AIMD study of the pressure induced structural and
dynamical changes in liquid Si, Delisle et al.79 were required to use different ion
pseudopotentials for the different thermodynamic states, each based on the refer-
ence gas density appropriate for that state. The effects of the reference system on

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the kinetic functional and the pseudopotential are mingled because the unscreening
of the effective potential involves the Ts [n]. A kinetic energy functional which takes
some account of the mainstay LR limit but which avoids a uniform reference system
is clearly desirable. The GGA form proposed by Perdew and Constantin60 might
meet this objective, but it awaits thorough testing and application. A modification
of the order-N averaged density electron kinetic energy functional in Eq. (4.22) to
render it insensitive to the choice of reference density is also a possibility. Some
progress can be made in the choice of neutral pseudo-atom pseudopotential which
makes it insensitive to the reference density and improves its transferability.
The norm conserving nonlocal pseudopotentials22,23 are transferable because the
conservation of the norm for each partial wave guarantees that the pseudopotential
scatters the same as the all-electron potential in an energy range about the valence
energy eigenvalue as well as at the energy. A corresponding requirement on the
local pseudopotential for use in the OF scheme and the all-electron potential can
be imposed. The energy dependence of each angular momentum component of
the scattering cross-section is replaced in the OF scheme by the dependence of the
pseudopotential on the chemical potential or mean electron density of the reference
system. If ∆Ez (n̄) is the cost in energy to insert the neutral atom with valence Z
into the cavity of radius R in the reference system with mean density n̄ then
Z
d∆Ez (n̄)
= − d~rφ0 (~r) (4.32)
dn̄ n̄0

where φ0 (r) is related to the Hartree potential φ(r) of the all-electron atom in the
gas. Specifically

φ(R) , r < R
φ0 (r) =
φ(r) , r > R

For cavities that fully enclose the atom core, the all-electron atom and the
pseudized atom will have the same φ0 (r), and so there is the possibility of shaping
the cavity to modify φ0 (r) and reduce the magnitude of d∆E z (n̄)
dn̄ |n̄0 or ideally have it
vanish. Presumably, a pseudopotential generated in this way would be transferable
and give energies that are insensitive to the reference density.
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4.3. OF-AIMD simulation of liquid metal systems

This section surveys our application of the OF-AIMD method to simple (sp bonded)
liquid metallic systems. The focus has been on the simple metals because the limita-
tions posed by the approximate kinetic functional and by the local pseudopotential
are least severe for these systems. The kinetic energy functional used in these
applications is the simplified version discussed earlier of the averaged density ap-
proach details of which are given in appendix A, and the local pseudopotential is our
adaptation of the neutral pseudoatom.77,78 However, the efficiency the OF-AIMD

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scheme allows the treatment of large samples for long simulation runs and realistic
treatments of the dynamics of bulk liquid metals and alloys can be performed.
This is the first subject of this section. The description of OF-AIMD simulations of
the liquid-vapor interface of several liquid simple metals and alloys completes the
section.

4.3.1. Bulk liquid simple metals and alloys


Research into the dynamical properties of liquid metals has produced a considerable
amount of both experimental and theoretical work.1 Comparatively, less attention
has been devoted to the dynamics of liquid binary alloys, although the last twenty
years have witnessed an increasing effort in this direction. Following a classical MD
study of liquid Na-K,80 the field was stimulated by the results of a MD simulation
of liquid Li4 Pb by Jacucci et al.,81 where a new, high-frequency mode, supported
by the Li atoms only (the so-called “fast sound”) was found. Subsequently, several
theoretical,82–86 computer simulations87–89 and experimental88,90–92 studies have
investigated the existence and properties of the collective excitations in liquid binary
systems.
During the last ten years, the OF-AIMD method has been extensively applied
to describe a wide range of static, dynamic and electronic properties in simple liq-
uid metals and binary alloys.27,65,79,93–97 Applications of the competing ab initio
method, the KS-AIMD approach, to these systems has been restricted almost en-
tirely to the study of the static properties. Even the calculation of the static prop-
erties in liquid binary alloys with moderate ordering tendencies poses enormous
computational challenges to the KS-AIMD approach because a proper description
of the local ordering requires simulations with a few thousand particles. Therefore,
most of the ab initio studies performed on the static properties in liquid binary
alloys have been done using the OF-AIMD method.
The study of dynamical, time-dependent properties usually requires simulations
lasting long enough so that the property of interest can be obtained for that time
interval in which it takes non-negligible values. This condition implies that several
thousand, even tens of thousand, configurations must be generated during the sim-
ulation run. Within the ab initio methods, this is a task which can be routinely
carried out at present by the OF-AIMD method. Even though some KS-AIMD
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calculations of dynamic properties have been performed, they ultimately rely on


the use of theoretical models for tackling the problems of noise and limited cor-
relation time, both related to the short simulation times affordable. In contrast,
OF-AIMD calculations of several dynamic properties, e.g. intermediate scattering
functions, dynamic structure factors, current correlation functions etc, have already
been performed for several simple liquid metals and binary alloys.
This section showcases the capability of the OF-AIMD simulation method for
treating the structural and dynamical properties of simple liquid metals and alloys.
A survey of the correlation functions and other quantities which are helpful in the

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interpretation of the dynamics is given next. These are quantities that can be
obtained from the MD simulations, some of which are accessible to experiment.
Results are then presented for liquid Mg, Ga and Si and the Ga-In liquid binary
alloy. These systems have been chosen because experimental data for static and/or
dynamic structure and some transport coefficients are available. Moreover, l-Ga and
l-Si are a challenging test of the approach because remnants of covalent bonding
are believed to persist into the liquid phase. The OF-AIMD method yields valence
electronic charge densities closely resembling covalent bonding.

4.3.1.1. Dynamic properties of liquids


The basic quantities for describing the dynamic properties of a fluid system are
the time correlation functions of several dynamic variables of the system. Relevant
dynamical variables are defined first and then their correlation functions will be
considered.
The self number density of particle j is defined as
~ j (t)) ,
ρs;j (~r, t) = δ(~r − R (4.33)

where R ~ j (t) denotes the position of particle j at time t. Its associated space Fourier
transform (FT) will be denoted as ρs;j (~q, t).
The number density of particles of a given type, is defined as the sum of all
the self number densities of particles of that type. We will assume throughout that
we are dealing with one-component systems; the generalization to multicomponent
mixtures is straightforward. The number density for a one-component system is
X
ρ(~r, t) = ~ j (t)) ,
δ(~r − R (4.34)
j

and its space FT will be denoted ρ(~q, t).


The current density of particles of a given type is also an important dynamic
variable, defined as
X
~j(~r, t) = V~j (t) δ(~r − R
~ j (t)) , (4.35)
j

~j (t) is the velocity of particle j at time t. The particle’s velocity itself is also
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where V
an important dynamic variable which will be considered later. The corresponding
space FT, ~j(~ q , t), is usually decomposed into a longitudinal (parallel to ~q) component
~jl (~
q , t) and a transverse (perpendicular to ~q) component ~jt (~q, t), with ~j(~q, t) =
~jl (q, t) + ~jt (q, t).
Other dynamic variables related to the dynamical properties of a system e.g. the
stress tensor, the energy current density, etc., will not be discussed here, instead,
the reader is referred to the many books and reviews on the subject, for instance
Refs. 1,15.

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The time correlation functions between dynamic variables are the basic quanti-
ties describing the dynamic properties. Particularly important are the time auto-
correlation functions of the dynamic variables introduced earlier.
The time autocorrelation function associated with ρs;j (~q, t) is the self interme-
diate scattering function

Fs (q, t) = h ρs;j (~q, t + t0 ) ρs;j (−~q, t0 ) i , (4.36)

where, for homogeneous and isotropic bulk systems, the average h· · · i is carried out
over time origins t0 , particles of the same type j, and directions of wave vector
~q. The FT to real space of Fs (q, t) is the van Hove self function Gs (r, t), which is
related to the probability that a given particle has moved a distance r in a time
interval t. The FT of Fs (q, t) into the frequency domain is the self dynamic structure
factor Ss (q, ω), which is directly related to the incoherent intensity obtained in an
INS experiment and so is accessible experimentally.
The intermediate scattering function is defined to be
1
F (q, t) = h ρ(~q, t + t0 ) ρ(−~q, t0 ) i , (4.37)
N
where N is the number of particles, and the average is now over time origins t0 and
directions of ~
q . This quantity contains information on the collective dynamics of
density fluctuations over the length and time scales. For multicomponent mixtures
p
the factor 1/N is replaced by 1/ Nα Nβ in the definition of Fαβ (q, t), where α and
β run from 1 to the number of different species and Nα is the number of particles of
species α. The FT to real space of F (q, t) is the van Hove function G(r, t), which is
related to the probability that if one particle is at the origin at a certain time, then
any particle (the same or a different one) will be at a distance r from the origin
after a time interval t. The FT into the frequency domain of F (q, t) is the dynamic
structure factor S(q, ω), which is also experimentally accessible, since it is directly
related to the coherent intensity obtained in an INS or IXS experiment. Finally we
note that F (q, t = 0) = S(q) is the static structure factor.
The longitudinal and transverse current correlation functions are defined to be
1 D~ E
Cl (q, t) = jl (~q, t + t0 ) · ~jl (−~q, t0 ) (4.38)
N

1 D~ E
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Ct (q, t) = jt (~q, t + t0 ) · ~jt (−~q, t0 ) . (4.39)


2N
The former is directly related to the intermediate scattering function, or, in the
frequency domain, to the dynamic structure factor
1 d2 F (q, t) ω2
Cl (q, t) = − , Cl (q, ω) = S(q, ω) , (4.40)
q2 dt2 q2
and can therefore be measured experimentally. However, the transverse current
correlation function, is not accessible by experiment and can only be determined by

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simulation. Its shape evolves from a Gaussian, in both q and t, in the free particle
limit (q → ∞), to a Gaussian in q for the hydrodynamic limit where q → 0 with
Ct (q → 0, t) = (1/βm) exp(−q 2 η | t | /M ρ) where η is the shear viscosity coefficient,
M is the ionic mass and ρ is the mean ionic number density. For intermediate q-
values Ct (q, t) has more complicated behavior.
Another correlation function, not directly accessible to experiment is the velocity
autocorrelation function, Z(t), and the closely related mean square displacement,
δr2 (t), of a given particle in the system
D E
Z(t) = V ~j (t + t0 ) · V
~j (t0 ) (4.41)

 2 
~ ~ j (t0 )
δr2 (t) = Rj (t + t0 ) − R
Z t
=2 dτ (t − τ )Z(τ ) , (4.42)
0

where, for a homogeneous bulk system the average is over time origins and particles
of the same type. Both functions are related to the diffusion coefficient, D, which
is a measurable quantity, either as the time integral of Z(t) or as 1/6 the slope of
δr2 (t) at long times.
These definitions are easily generalized to multi-component mixtures. For exam-
ple, for a binary mixture there appear the partial intermediate scattering functions,
Fαβ (q, t) whose FT into the frequency domain give the partial dynamic structure
factors, Sαβ (q, ω). Fαβ (q, t = 0) = Sαβ (q) are the partial static structure factors.
The total static structure factor, ST (q), the quantity usually measured by neutron
diffraction, is a weighted combination of the Sαβ (q).

4.3.2. Liquid Mg
Starting with the pioneering work of Madden and coworkers,54 the OF-AIMD
method has been used to calculate static, dynamic and electronic properties in sim-
ple liquid metals. Here we report the results for l-Mg because the sort of agreement
with experiment is typical of that obtained for other liquid simple metals.
Mg is the simplest alkali-earth metal, but the group has not attracted much
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experimental work because of technical difficulties related to the high chemical


reactivity and to gas adsortion.98 Only a few properties have been measured, e.g.
the static structure,99,100 density,101 sound velocity,102 electrical resistivity,103 and
thermopower.104 Consequently, in comparison with the alkalis or some polyvalent
metals theoretical work has been scarce. However, recent experiments on bulk liquid
Mg (l-Mg) have measured the static100 and dynamic105 structure factors.
Liquid Mg near its triple point has been studied by the OF-AIMD
method.93,97,106 Here we report the recent simulations of Sengul et al.,97 with
T =953 K and ρ = 0.03829 Å−3 , and using 2000 particles, a timestep of 2.5 fs and

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a total averaging time of 50 ps after equilibration. The cutoff energy was 13 Ryd-
bergs and the number of planewaves was around 145000. In comparison, the only
KS-AIMD simulation performed thus far for this system107,108 used 90 particles, a
non-local pseudopotential, a total averaging time of 1.8 ps, a cutoff energy of 12
Rydbergs resulting in 500000 planewaves. Moreover, only some static properties
were computed – dynamic ones would have required substantially longer simulation
times. This highlights the important computational advantages of the OF-AIMD
scheme, specially for the evaluation of time dependent quantities.

3
1
Sie(q)
2 0.5
S(q)

3 4 5
0
1

-0.2
0
2 -1 4 6
q (Å ) 0 2 4 6
-1
q (Å )
Fig. 4.1. S(q) of l-Mg at 953 K. Open cir-
cles: experimental XD data from Waseda.99 Fig. 4.2. Sie (q) of l-Mg at 953 K. Contin-
Triangles and squares: experimental XD uous line: present OF-AIMD simulations.
and ND data at 973 K from Tahara et Triangles: KS-AIMD simulation data from
al.100 Continuous line: OF-AIMD simu- de Wijs et al.107,108 Dash-dotted line: ex-
lations. The inset shows the second peak perimental data of Tahara et al.100
region, where Waseda’s XD (Tahara’s ND)
data have been displaced downwards (up-
wards) by 0.2 units.

Figure 4.1 shows the calculated static structure factor S(q) along with the XD
data of Waseda99 and the more recent (XD and ND) data of Tahara et al.100 The
OF-AIMD results closely follow experiment, especially the position (qp ) and height
of the main peak as well as the asymmetric form of the second peak which is shown
in the inset of Fig. 4.1. Similar good agreement was also found for the S(q) obtained
U.S. or applicable copyright law.

from the KS-AIMD simulations.107,108


The simulation also gives the pair distribution function, g(r), whose main peak’s
position, rp , is usually taken to be the average nearest neighbor distance. The OF-
AIMD gives rp ≈ 3.10 Å, close to the experimental value99 of ≈ 3.09 Å. A related
quantity is the radial distribution function (RDF), G(r) = 4πr2 ρg(r), which gives
the distribution of particles around a given one taken as the origin. The number
of nearest neighbors, the coordination number (CN), is obtained by integrating
G(r) up to a distance rm which is usually taken to be the position of its first
minimum,109,110 giving CN ≈ 12.3 atoms/ions.

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The ion-valence electron structure factor, Sie (q) providing information on the
distribution of valence electrons around the nuclei is simple to calculate from an
ab initio simulation, but its experimental measurement is difficult. The Sie (q) is
depicted in Fig. 4.2 which shows good agreement between the KS-AIMD and OF-
AIMD results, and both reproducing rather well the trends in the experimental
data.100

0.1
S(q,ω)/S(q)

-1 -1
q=0.35 Å q=0.59 Å
0.05 q = 1.89 Å
-1 -1
q = 3.11 Å
0.03

0
-1 -1
q=0.82 Å q=1.35 Å 0
-1 -1
q = 2.35 Å q = 2.66 Å
0.02 0.05

0
0 20 40 0 20 40 60 0
-1 0 20 40 0 20 40
ω (ps ) -1
ω (ps )
Fig. 4.3. S(q, ω) for l-Mg at T = 953 K. Full
Fig. 4.4. Same as in the previous graph
circles: experimental IXS data at 973 K.105 Full
but for q = 1.89, 2.36, 2.66 and 3.12 Å−1 .
and dashed lines: OF-AIMD results for q =
0.34, 0.61, 0.82 and 1.36 Å−1 , after and before con-
volution with the experimental resolution function
respectively.

The calculated dynamic structure factors, S(q, ω), are shown in Figs. 4.3–4.4 for
a representative range of wavevectors. Up to q ≈ (3/5) qp , the S(q, ω) show well
defined sidepeaks indicative of collective density excitations. A proper compari-
son with the measured IXS data105 requires the prior convolution of the calculated
U.S. or applicable copyright law.

S(q, ω) with the experimental resolution function105 and the inclusion of the de-
tailed balance factor.1 Once both are included, there is good overall agreement
with experimental IXS data although for small q’s, there is some underestimation
of the quasielastic contribution. From the positions of the sidepeaks, ωm (q), the
dispersion relation of the density fluctuations is obtained and the result is shown in
Fig. 4.5 along with ωl (q), which is the dispersion relation derived from the maxima
of the longitudinal current correlation function, Cl (q, ω) = ω 2 S(q, ω). Also shown
is the experimental ωl (q) data105 and the line representing the dispersion of the
hydrodynamic sound whose slope gives the experimental111 bulk adiabatic sound

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40
ωm(q), ωl(q) (ps )
-1

20
20

Γ(q) (ps )
-1
10

0
0 1 2 3
-1 0 1 2 3
q (Å ) -1
q (Å )
Fig. 4.5. Dispersion relation for l-Mg at T =
953 K. Open circles: peak positions, ωm (q), Fig. 4.6. Full (open) diamonds with error
from the calculated S(q, ω). Open squares: lines: experimental (calculated) values for the
peak positions, ωl (q), from the maxima of the HWHM, Γ(q), of the inelastic peaks in l-Mg
calculated longitudinal current, Cl (q, ω). Full at T = 953 K.
circles: experimental ωm (q) at T = 973 K from
Kawakita et al.105 Full line: Linear disper-
sion with the hydrodynamic sound velocity,
v = 4050 m/s.

velocity cs = 4050 m/s at T=953 K. In the hydrodynamic region, the slope of the
dispersion relation gives a q-dependent adiabatic sound velocity, cs (q), which in the
limit q → 0 reduces to the bulk adiabatic sound velocity. The calculated ωm (q),
gives a value for the adiabatic sound velocity cs = 4200 (± 150) m/s in reasonable
agreement with the experiment.
Another quantity characterizing the collective density excitations is the half
width at half height (HWHM) of the inelastic peak, Γ(q), which provides infor-
mation on the lifetimes of the excitations. Figure 4.6 shows the calculated and
experimental data105 for Γ(q).
Figure 4.7 shows the calculated Ct (q, t) and Ct (q, ω) for a range of q-values. At
the smallest q-value allowed by the simulation (q = 0.168 Å−1 ≈ 0.07qp ) Ct (q, t)
U.S. or applicable copyright law.

already has a weak oscillatory behaviour. The associated spectrum, Ct (q, ω), for
some intermediate q-range shows an inelastic peak existing at the smallest value
reached by the simulation which is a signature of the propagation of shear waves in
the liquid. The shear viscosity can be calculated from Ct (q, t). A value of η=1.35 ±
0.15 GPa ps is obtained which is in fair agreement with the experimental value112
ηexp ≈ 1.16 GPa ps.
The velocity autocorrelation function (VACF) obtained by OF-AIMD is plotted
in Fig. 4.8. The shape typical of high density systems1,27,65 such as simple liquid
metals near melting is seen, which can be explained in terms of the so-called “cage

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4 5
0.23
0.60 1

Z(ω)
1.36 4
3
Ct(q, t)/Ct(q, t=0)

2.35
3.50 0.01

Ct(q, ω)
5.0 3
2 0.5

Z(t)
0
2 0 30 -1 60
ω (ps )
1
0
1

0
0 -0.4
0 0.3 0.6 0 30 60 0 0.2 0.4
t (ps) -1 t (ps)
ω (ps )
Fig. 4.8. Full line: Normalized
Fig. 4.7. OF-AIMD calculated transverse current corre-
velocity autocorrelation function,
lation function, Ct (q, t), and its spectra, Ct (q, ω), at sev-
Z(t), of l-Mg at 953 K. The in-
eral q-values (in Å−1 ) for l-Mg at T = 953 K and q = 0.23
set represents its power spectrum
(full curve), q = 0.60 (dotted curve), q = 1.36 (dashed
Z(ω).
curve), q = 2.35 (dash-dotted curve), q = 3.50 (dash-
double dot curve), q = 5.0 (full circles)

effect”, in which a tagged particle is enclosed in the cage formed by its neighbors.
The Z(t) exhibits oscillatory behaviour with a distinct negative minimum at ≈ 0.1
ps followed by rapidly decaying oscillations. An estimate of the frequency at which
a given atom is vibrating within the cage1,7 can be obtained from the short time
2 2
expansion Z(t) = 1 − ωE t /2 + · · · , where ωE is the so-called “Einstein frequency”
of the system. The OF-AIMD result is ωE ∼ 30.0 ps−1 which is comparable to
ωE ∼ 30.5 ps−1 estimated by Kawakita et al. from their experimental data.105 The
self-diffusion coefficient, D, is deduced from the time integral of Z(t) giving a value
DOF−AIMD = 0.51 Å2 /ps. Although no experimental data are available, we note
that the KS-AIMD simulation of Wijs et al.107 gave DKS−AIMD = 0.50 Å2 /ps.

4.3.3. Liquid Ga
Gallium is an interesting material with unusual structural and electronic proper-
ties. It has a low melting point (303 K) and exhibits a variety of morphological
crystalline structures including both covalent and metallic bondings. At ambient
U.S. or applicable copyright law.

pressure,113,114 the stable crystalline structure is the orthorhombic α-Ga with seven
near neighbors; the nearest one at 2.48 Å is covalently bonded, two second neigh-
bors are at 2.69 Å, two third at 2.73 Å, and two fourth neighbors at 2.79 Å. Upon
application of pressure it transforms to the metallic face-centered tetragonally dis-
torted Ga II. At melting, l-Ga has a higher density than the solid α-Ga and its local
structure is similar to that of Ga II. Moreover, its static structure factor, S(q) has
a main peak with a shoulder characteristic of non-closed packed structures.
Two early KS-AIMD simulations of bulk l-Ga used 64 particles and the LDA for
the exchange and correlation. The first performed by Gong et al.115 for T =1000K

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used a separable pseudopotential and obtained electronic and static properties. The
second for l-Ga at T = 702 K and 982 K of Holender et al.116 used a norm conserv-
ing nonlocal pseudopotential and yielded some results for the dynamical structure
factor.
These ab initio studies provided insights into the valence electronic charge densi-
ties. It was suggested115 that metallic and covalent characters coexist in l-Ga, with
the latter one represented by the appearance of some very short lived Ga2 covalent
molecules with bonds similar to those of α-Ga. However, these KS-AIMD studies
were performed at high temperatures, far above the region near the melting point
where most experimental data is available.
Recently, OF-AIMD simulations have been performed for bulk l-Ga at several
thermodynamic states. Here we report results for two temperatures and ion number
densities: T = 373 and 959 K and ρ = 0.0512 and 0.0490 Å−3 respectively. The
simulations used 2000 ions in a cubic cell with periodic boundary conditions, an
equilibration time of 15 ps followed by 80 ps over which properties were averaged.
For comparison we comment that the two KS-AIMD simulations cited above lasted
2.5 ps.
Figure 4.9 shows the calculated static structure factors, S(q), along with the ND
data of Bellissent-Funel et al.117,118 The calculated S(q) at T = 373 K, has a main
peak at qp ≈ 2.51 Å−1 and the characteristic shoulder at ≈ 3.10 Å−1 . Comparison
with the ND data117,118 reveals some overestimation of the height of the main peak,
but the amplitude and phase of the subsequent oscillations are well reproduced. The
calculated S(q) at T = 959 K shows very good agreement with experiment, similar
agreement to that of the previous KS-AIMD results.115,116
The calculated OF-AIMD g(r) has a main peak at rp ≈ 2.81 Å for T = 373 K,
which reduces to ≈ 2.73 Å for T = 959 K yielding CN values of ≈ 11.8 and
8.5 atoms/ions respectively. This reduction in rp is in good agreement with the
experimental results: 2.77 and 2.71 Å leading to CN ≈ 10.5 and 8.7 atoms for T =
326 and 959 K respectively. The KS-AIMD results at T = 1000 and 982 K gave
CN ≈ 8.9 and 9.1 respectively.115,116
Figure 4.9 shows the bonded-atoms structure factor, S(q, rb ), calculated by con-
sidering only those atoms with one or more neighbors within a distance rb . The
S(q, rb ) are shown for several rb values. For T = 959 K the main peak of S(q, rb ) for
rb ≤ 2.38 Å is at the position of the shoulder of the full S(q), but around rb = 2.38 Å
U.S. or applicable copyright law.

a second peak emerges at a smaller q value, which grows as rb increases, to become


the main peak of S(q). This feature was noted in the KS-AIMD simulations115 of
l-Ga at 1000 K and suggests that the shoulder in S(q) is related to the existence
of ions separated by distances less than ≈ 2.38 Å. Moreover, the KS-AIMD simula-
tions showed that for these separations there is an accumulation of electron density
along the line joining the atoms akin to the bonding charge in the Ga2 dimers found
in solid α-Ga, and it suggested that the shoulder in S(q) is related to the survival
of these “molecules” after melting, which although short-lived are appreciable in

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5 373 K 959 K

full full
4
2.78 2.78
S(q,rb)

3 2.68 2.68
2.58 2.58
2 2.48 2.48
2.38 2.38
1 2.28

0
1 2 3 4 5 6 1 2 3 4 5 6 7
-1 -1
q (Å ) q (Å )

Fig. 4.9. Bonded-atoms structure factors of l-Ga for different cutoff radii, rb . The total S(q)
corresponds to upper curves at both temperatures. Full circles: experimental ND data.117,118 at
T = 363 K and 959 K.

number.115 Similar trends are obtained for the variation of S(q, rb ) with rb at the
lower temperature, T = 373 K. The shoulder of S(q) is at the position of the main
peak of S(q, rb ) for small rb , but a second peak at lower q emerges around rb = 2.38
Å and develops into the main peak of S(q).
P
The RDF can be decomposed asR110 G(r) = i Gi (r) where the Gi (r) is the
r
partial RDF whose integral Pi (r) = 0 Gi (s)ds, gives the probability of finding the
i-th neighbor at a distance ≤ r. The limits Pi (0) = 0 and Pi (∞) = 1 are attained
at finite distances rimin and rimax which define the spherical shell where the i-th
neighbor sits. In particular, r1min is the distance of closest approach between two
atoms. The OF-AIMD results show a noticeable displacement of G1 (r) to smaller
distances at the higher temperature, with r1min moving from 2.25 at 373 K to 2.13 Å
at 959 K, while r1max ≈ 2.90 forR both temperatures. From the G1 (r) the average
R
concentration, x(R) = P1 (R) = 0 G1 (r) dr, of atoms whose first neighbor is closer
than a distance R can be computed.
U.S. or applicable copyright law.

The KS-AIMD simulations115 of l-Ga at 1000 K yielded for a typical covalent


bonding distances, R = 2.35 Å, a value x(R) ≈ 0.05 − 0.10, whereas the OF-AIMD
simulations at 959 K give x(2.28) = 0.04 and x(2.38) = 0.18. These “covalently
bonded” atoms have been interpreted as short-lived “molecules” mainly responsi-
ble for the shoulder in the S(q). It was also predicted that the concentration of
“molecules” should increase at lower temperatures leading to a sharper shoulder.
However, the OF-AIMD results for T = 373 K give a larger distance of closest
approach and smaller values x(2.28) ≈ 0 and x(2.38) = 0.03. This result brings
into question the interpretation that these atoms form “molecules”, even though

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0.025

electron density (e/a.u. )


ρOF-ρsup

3
0.015 0.02
0.015
0.015
959 K
0.015 0.01 373 K

0.005
0
-0.005
2.2 2.4 2.6 2.8 3 3.2
Fig. 4.10. Electron density for a selected r (Å)
triplet of Ga atoms at 373 K. Left panel: OF
density. Right panel: KS density. The con- Fig. 4.11. Difference between the OF den-
tour lines are plotted for values of the den- sity and the superposition obtained from the
sity equal to 0.010 electrons/(a.u.)3 (the min- LR screened pseudopotential, at its maxi-
imum inside the peanut-shaped line in the mum value between two atoms separated by
right part of the KS data) and increments of a distance r. The atoms considered in the
0.005 electrons/(a.u.)3 . plot are those with a neighbor within 2.38 Å,
and their first, second and third neighbors.

the shoulder in S(q) is sharper at the lower T . It may be that the relevant signa-
ture defining these “molecules” is not the ion separation but the accumulation of
electronic density between them. There is a triplet in α-Ga with distances between
the central and outer atoms of 2.48 and 2.69 Å and a bond angle of 106◦ , and we
have found a very similar triplet in l-Ga with distances of 2.35 and 2.55 Å and a
bond angle of 103◦. For the triplet in l-Ga we have calculated the electron density
using both OF-AIMD and KS-AIMD simulation methods and obtained the density
contours plotted in Fig. 4.10. The overall agreement is remarkable although there
are some differences, for instance in the lower-right corner or to the right where
the KS-AIMD density shows a somewhat smaller minimum than the OF-AIMD
one. However, the OF-AIMD method tends to overestimate the electron density
between the atoms, suggesting even stronger “bonds”, if bonds they are, than those
obtained with the KS-AIMD.
A good approximation to the electron density for a simple metal is given by
the superposition of pseudoatom densities obtained from LR screening of the pseu-
dopotential. This superposed density increases between the atoms as they come
closer. An analysis of the OF-AIMD density between pairs of atoms including first,
U.S. or applicable copyright law.

second and third neighbors shows that the charge accumulation depends strongly
on the distance between the atoms and the smaller the separation, the stronger the
effect. But this accumulation clearly exceeds that of the superposed densities for
small separations and approaches the superposed density as the atoms separate for
both temperatures, as shown in Fig. 4.11. This correlation between distance and
bonding charge suggests using the distance between two atoms to identify them as
bonded.
Turning now to the dynamic properties, for both states the calculated S(q, ω)
show side peaks persisting up to q ≈ (3/5)qp . The dispersion relation of the den-

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sity fluctuations obtained from the positions of the sidepeaks, ωm (q), provides an
estimate of the adiabatic sound velocity, cs . For T=373 K we have obtained cs =
2920 ± 150 m/s, which is close to the experimental result119 of cs = 2890 ± 50 m/s.
Hosokawa et al.120 have measured the q-dependent adiabatic sound velocity, cs (q)
= ωl (q)/q, where ωl (q) is the maximum frequency of the longitudinal current corre-
lation function, Cl (q, ω). Also, Scopigno et al.121 have measured cs (q) for a slightly
smaller temperature of T= 315 K. Both sets of data are plotted in Fig. 4.12. The
OF-AIMD results for the higher temperatures, T=523 and 959 K, are cs = 2875
and 2750 ± 150 m/s, which are close to the respective experimental values,119 cs =
2840 and 2700 ± 50 m/s.

3 <
<
cs(q) ( 10 m/s)

1
3

2 373 K
523 K
959 K
0.5
Z(t)

0
0 -0.2
0 1 2 0 0.4 0.8
-1 t (ps)
q (Å )
Fig. 4.13. Normalized OF-AIMD
Fig. 4.12. q-dependent sound velocity cs (q) for l-
Z(t) for l-Ga at three temperatures
Ga. Open circles: OF-AIMD results. Full circles:
along the coexistence line.
experimental cs (q) at T=373 K from Hosokawa et
al.120 Crosses: experimental cs (q) at T=315 K from
Scopigno et al.121 Dashed line: OF-AIMD results for
T=959 K. The arrows show the experimental adia-
batic sound velocities of 2890 m/s. and 2700 m/s. for
T = 373 K and 959 K respectively.
U.S. or applicable copyright law.

The calculated Ct (q, t) show, at low and intermediate q-values, an oscillatory be-
haviour which becomes weaker with increasing temperature. The associated spectra
display inelastic peaks within a range (0.3 Å−1 ≤ q ≤ 2.30 Å−1 for T = 373 K) which
narrows as the temperature is increased and at T = 959 K the inelastic peaks have
disappeared. The shear viscosity coefficient has been evaluated from the Ct (q, t)
and the results are (in GPa ps units) η = 1.60±0.20 (for T = 373 K), η = 1.12±0.15
(T = 523 K) and η = 0.74 ± 0.08 (T = 959 K) which are in reasonable agreement
with the experimental data,122 namely ηExp = 1.58 ± 0.05, ηExp = 1.10 ± 0.05 and
ηExp = 0.63 ± 0.03 GPa ps.

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The calculated VACF’s are depicted in Fig. 4.13 for the different temperatures.
They exhibit the usual pattern for the simple liquid metals: (i) oscillatory behaviour
with a distinct negative minimum followed by weaker oscillations and (ii) these
features dampened with increasing temperature i.e. decreasing density. The time
integral of the VACF gives the self-diffusion coefficient and the calculated values are:
DOF−AIMD = 0.20 ± 0.02, 0.38 ± 0.02 and 0.95 ± 0.04 Å2 /ps for T = 373, 523 and
959 K respectively. The experimental results111 for l-Ga at melting (T = 303 K) lie
within the range DExp ≈ 0.16 − 0.17 Å2 /ps and extrapolation to T = 373 K gives
an estimate DExp ≈ 0.24 − 0.27 Å2 /ps. No experimental data are available for the
higher temperatures, but we may compare with other calculations. For example, the
KS-AIMD calculation at T = 1000 K of Gong et al.115 gave DKS−AIMD = 1.0 Å2 /ps,
which is very close to the present OF-AIMD result. However, the KS-AIMD study
of Holender et al.116 at T=982 K gave the much smaller value DKS−AIMD = 0.65
Å2 /ps. All in all, the OF-AIMD results are within the range of values predicted by
the KS-AIMD method.

4.3.4. Liquid Si
Si also has interesting properties which, together with its technological importance,
has stimulated intensive theoretical123–133 and experimental99,134–139 work. Its
high-density forms include crystalline, amorphous and liquid phases with the former
two being covalently bonded and semiconducting and the latter one metallic. Upon
melting Si undergoes a semiconductor-metal transition along with a density increase
of ≈ 10% and important changes in the local atomic structure. This evolves from
an open one, with a fourfold tetrahedral coordination, to a more compact liquid
structure with an approximate sixfold coordination.140,141 In c-Si the semiconduct-
ing diamond structure contracts with pressure and transforms at 12 GPa to the
metallic white-tin structure142 and then to the metallic simple hexagonal structure
at 16 GPa.143 This has led to the suggestion that l-Si might consist of a mix-
ture of diamond-type and white-tin-type structures with the fraction of the latter
increasing with pressure.
The S(q) of l-Si near the triple point has been measured by both XD and
ND.99,134–136 More recently, Funamori and Tsuji141 have performed XD experi-
ments to measure the S(q) of l-Si at pressures of 4, 8, 14 and 23 GPa and temper-
U.S. or applicable copyright law.

atures about 50 K above the melting point for each pressure. From their analysis
of the data, Funamori and Tsuji141 have concluded that l-Si up to 8 GPa has a
local structure intermediate between the diamond-type and the white-tin-type but,
between 8 and 14 GPa drastic structural changes occur and l-Si transforms to a
denser structure.
Stich et al.130,131 performed the first KS-AIMD calculation for l-Si near the
triple point using 64 particles, a non-local pseudopotential22 and the LDA for ex-
change and correlation. Subsequently, a more comprehensive study was reported132
with 350 particles and a GGA for exchange and correlation. Another KS-AIMD

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An Orbital Free ab initio Method: Applications to Liquid Metals and Clusters 85


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calculation near the triple point has been performed by Godlevsky et al.133 using 64
ions and a non-local, pseudopotential.23 These ab initio studies provided accurate
insights into the static structure and the valence electron charge densities, how-
ever the inherent strong computational demands prevented the study of dynamical
properties. The extensive OF-AIMD simulations of Delisle et al 79,96 for bulk l-Si
at several thermodynamic states as listed in Table 4.1 allow study of dynamical
properties.
The simulations used 2000 ions, an equilibration time of 10 ps and the calculation
of properties was made averaging over 50-65 ps. The three KS-AIMD simulations
cited above lasted for a time 0.9-1.2 ps.

4 GPa 8 GPa
2
2
S(q)

1
S(q)

1
0
14 GPa 23 GPa
2
0
0 5 10
-1
q (Å ) 1

Fig. 4.14. Static structure factor of l-Si


near the tripe point. Open circles: ex- 0
0 4 8 0 4 8
perimental ND data.134 Full circles: ex- -1
perimental XD data.135,136 Continuous
q (Å )
line: OF-AIMD simulations
Fig. 4.15. Static structure factor of l-Si at differ-
ent high pressures. Full circles: experimental XD
data.141 Continuous line: OF-AIMD simulations.

Figure 4.14 shows the calculated S(q) along with the experimental data.134–136
The OF-AIMD S(q) accounts for the position and height of the main peak, but the
amplitudes of the following peaks and troughs are underestimated. The shoulder
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on the high-q side of the main peak is reproduced although with a smaller height.
It will be recalled that very similar shortcomings are seen in the S(q) obtained from
the KS-AIMD simulations of Stich et al.,130–132 whereas that of Godlevsky et al.
gives a shoulder whose height is comparable to the main peak.133 The calculated
S(q) for l-Si under pressure are shown in Fig. 4.15 along with the experimental XD
data.141 The experimental S(q) show that as pressure increases, the main peak
grows in intensity and shifts to larger q monotonically whereas the second peak’s
position decreases between 8 and 14 GPa. Meanwhile, the distinctive shoulder at
the high-q side of the main peak shrinks and practically vanishes by 23 GPa. These

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86 A. Aguado et al.
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features are qualitatively reproduced by the OF-AIMD S(q)’s although there are
some quantitative discrepancies i.e. the OF-AIMD S(q) overestimate the intensity
of the main peak while slightly underestimating that of the shoulder.
Funamori and Tsuji141 have argued that l-Si undergoes a high pressure structural
transformation between 8 and 14 GPa. Whereas, l-Si contracts with pressure up
to at least 8 GPa by reducing the bond length (quantified by rp ), the increase
in rp between 8 and 14 GPa does suggest a structural change with a qualitative
increase in the CN. Table 4.1 lists CN values obtained from OF-AIMD simulations
along with corresponding experimental data.135,137,141 Notice that CN grows with
compression with an abrupt increase from 8 to 14 GPa. A similar sharp increase
was also deduced by Funamori and Tsuji141 from their experimental RDF.

Table 4.1. Thermodynamic states of l-Si studied by the OF-AIMD simula-


tions along with the results obtained for several magnitudes. ρ is the total
ionic number density, T is the temperature, CN is the coordination number, cs
is the adiabatic sound velocity (± 150 m/s), D is the self-diffusion coefficient
and η is the shear viscosity coefficient.

P (GPa) ρ (Å−3 ) T (K) CN cs (m/s) D (Å2 /ps) η (GPa ps)

0 0.0555 1740 6.0 4250 2.28 ± 0.05 0.75 ± 0.10


4 0.0580 1503 6.6 5100 1.82 ± 0.05 0.77 ± 0.10
8 0.0600 1253 7.2 5400 1.33 ± 0.05 0.84 ± 0.10
14 0.0670 1093 9.6 6300 0.70 ± 0.03 1.47 ± 0.15
23 0.0710 1270 11 6750 0.70 ± 0.03 1.55 ± 0.15

The calculated partial RDF, G1 (r), gives a distance of closest approach, r1min ≈
1.9 Å at ambient pressure, and a slight increase to a common value of 2.0 for
l-Si at the higher pressures. The width of the first neighbor shell narrows with
pressure, leading to narrower and higher G1 (r) functions, with a marked change
between 8 and 14 GPa further supporting the idea of a structural transition between
these pressures. Analysis of the bonded-atoms structure factor, S(q, rb ), for all the
thermodynamic states shows the same pattern as l-Ga. For small values of rb there
is a peak at the position of the shoulder of S(q), while at larger rb values a feature
emerges that develops into the main peak of S(q) as rb is increased. Those rb -values
for which the feature at the position of the main peak of S(q) starts developing are
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2.20, 2.25, 2.22, 2.19 and 2.16 Å corresponding to 0, 4, 8, 14 and 23 GPa states
respectively.
The electron density in a plane containing a triplet of atoms again helps to vi-
sualize the degree of “covalency”, and the OF-AIMD results are compared with the
KS-AIMD calculations in Fig. 4.16. The distances (in Å) between the central and
outer atoms are 2.14 and 2.25 (for 0 GPa), 2.08 and 2.21 (for 4 GPa), 2.21 and 2.23
(for 8 GPa), 2.14 and 2.25 (for 14 GPa) and 2.15 and 2.24 (for 23 GPa) and the
respective bond angles are 111, 106, 107, 99 and 101 degrees. The overall agreement
between the OF-AIMD and KS-AIMD electron densities is again impressive and in

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