Академический Документы
Профессиональный Документы
Культура Документы
May not be reproduced in any form without permission from the publisher, except fair uses permitted under
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
RECENT PROGRESS IN
ORBITAL-FREE DENSITY
FUNCTIONAL THEORY
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory1
8633hc_9789814436724_tp.indd 9/10/12 2:08 PM
Account: s6777224
Recent Advances in Computational Chemistry
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
Recent Advances in Computational Chemistry – Vol. 6
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
RECENT PROGRESS IN
ORBITAL-FREE DENSITY
FUNCTIONAL THEORY
edited by
Tomasz A Wesolowski
University of Geneva, Switzerland
World Scientific
NEW JERSEY • LONDON • SINGAPORE • BEIJING • SHANGHAI • HONG KONG • TA I P E I • CHENNAI
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory2
8633hc_9789814436724_tp.indd 9/10/12 2:08 PM
Account: s6777224
Published by
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
2012046733
For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center,
Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from
U.S. or applicable copyright law.
the publisher.
Printed in Singapore.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
Preface
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
vi Preface
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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-
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
Preface vii
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz
viii A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
Contents
Preface v
ix
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
x Contents
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
13. Analytic Approach and Monte Carlo Sampling for Electron Correlations 369
L. M. Ghiringhelli & L. Delle Site
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
Contents xi
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz
xii A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
PART 1
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz
1 A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 0
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz
2 A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
Chapter 1
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
U.S. or applicable copyright law.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 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:
hδρ(r)i ≡ 0 . (1.4)
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
KS
δ(Ev [ρKS ] − Ts [ρKS ]) δVs [ρKS ]
veff (r) = = . (1.9)
δρKS (r) δρKS (r)
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
N
X 2
ρKS (r) = |φKS
i (r)| , (1.10)
i=1
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
N
X 2
ρ0 (r) = |φLL
i (r)| . (1.14)
i=1
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
After introducing Eqs. (1.5), (1.10), and (1.12), Kohn and Sham partitioned Ev [ρ]
into two main pieces:2
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
i=1
N
X N
X
=2 δφi (r)t̂φi (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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
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.
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.
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)
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
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)
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)
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
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
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
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)
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
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
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).
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
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
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 1
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
Chapter 2
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.
2.1. 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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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-
U.S. or applicable copyright law.
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-
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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]
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
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
U.S. or applicable copyright law.
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:
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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 .
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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
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
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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:
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:
where:
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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)).
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 6, 2012
Table 2.1. Variational estimates for the KS kinetic energy from an LDA (SVWN) density of N2 . Values in a.u.
15:59
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses
Table 2.2. Variational estimates for the KS kinetic energy from a HF density of N2 . Values in a.u.
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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
U.S. or applicable copyright law.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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
U.S. or applicable copyright law.
Financial support from the National Science Foundation (WY) and the Office of
Naval Research (FAB) is gratefully acknowledged.
References
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 2
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz
30 A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
Chapter 3
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
January 23, 2013 16:0 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
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 −∞
σ = κ−1
T `, (3.5)
and March.18
The basic variational principle on which the TFvW method is founded takes the
form
δ(E − N µ) = 0 (3.6)
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
∂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,
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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).
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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’
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
(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 .
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
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
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/~.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
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
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-
U.S. or applicable copyright law.
1 2
t(r) = tvW (r) + ρ (∇θ(r))
2
~2 (∇ρ)2 1 2
= + ρ (∇θ(r)) . (3.51)
8m ρ 2
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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)
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
Table 3.1. Ionization potentials in a.u. and fitted parameters for the atoms studied. After
Ref. 36.
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)
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
U.S. or applicable copyright law.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
U.S. or applicable copyright law.
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 3
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz
54 A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
Chapter 4
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
56 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
58 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
60 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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.
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,
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
62 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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
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.
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
64 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
66 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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
U.S. or applicable copyright law.
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
68 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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)
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
U.S. or applicable copyright law.
further study.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
January 23, 2013 16:0 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
70 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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.
U.S. or applicable copyright law.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
72 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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.
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
~j (t) is the velocity of particle j at time t. The particle’s velocity itself is also
U.S. or applicable copyright law.
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
74 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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
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
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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
U.S. or applicable copyright law.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
76 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
78 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
80 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
82 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
0.025
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-
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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.
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
84 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
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
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
U.S. or applicable copyright law.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224
December 7, 2012 15:36 World Scientific Review Volume - 9.75in x 6.5in master˙16-11-12/Chp. 4
86 A. Aguado et al.
Copyright © 2013. World Scientific. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
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.
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
U.S. or applicable copyright law.
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
EBSCO Publishing : eBook Academic Collection Trial - printed on 8/24/2018 11:35 AM via UNIVERSIDAD
PONTIFICIA BOLIVARIANA BUCARAMANGA
AN: 575385 ; Wang, Yan Alexander, Wesolowski, Tomasz A..; Recent Progress In Orbital-free Density
Functional Theory
Account: s6777224