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xI (t )
d 2 RI
MI 2
FI
dt
t t
1 FI
(1) RI (t t ) RI (t ) vI (t )t t 2 O(t 3 )
2 MI
1 FI
(2) RI (t t ) RI (t ) vI (t )t t 2 O(t 3 )
2 MI
FI
(1) (2) RI (t t ) RI (t t ) 2 RI (t ) t 2 O(t 4 )
MI
Verlet’s algorithm
FI
RI (t t ) 2 RI (t ) RI (t t ) t 2 O(t 4 )
MI
A typical molecular dynamics protocol
1
T
A A( R(t ), P(t )) dt A
A( R, P) exp( E ) dRdP
T0
exp( E)dRdP
Average in Molecular Dynamics = Average in Statistical Mechanics
Molecular Dynamics
“Molecular dynamics”
for atoms
Ma = F = -dE/dR
Schroedinger equation
for electrons
Hy Ey
R. Cohen e--e- interactions:
Density Functional Theory
e--nuclei interactions:
Pseudopotentials
d 2 RI dE ({R}) e-
MI 2
FI e-
dt dRI e-
Electrons respond much faster than e-
nuclei to external forces, because of e-
their lighter mass, therefore: Nuclei
e-
ER y e H e Ry e
nuclear positions {R}
Consequence:
Every MD step requires the
calculation of the QM ground
state of the electrons
Density functional theory
Electron-electron (many-body)
interaction
d 2 RI dE ({R}) d y 0 H e ({R})y 0
MI 2
FI
dt dRI dRI
d y 0 H e ({R})y 0 dH e ({R}) dy 0 dy 0
y0 y0 H e ({R})y 0 y 0 H e ({R})
dRI dRI dRI dRI
dH e ({R}) dy 0 dy 0
y0 y 0 E ({R}) y 0 E ({R}) y 0
dRI dRI dRI
dH e ({R}) d y0 y0
y0 y 0 E ({R})
dRI dRI
Forces can be calculated without
dH e ({R})
y0 y0 recalculating the ground state
dRI wave function for small atomic
displacements
The Born Oppenheimer
Dynamics
How to keep electron in the ground state (1)
d 2 RI dE ({R})
MI FI
dt 2 dRI
E ({R}) y 0 H e ({R})y 0
y cii
i
y H e y ci c*j i H e j
i, j
d 2 RI dE ({R})
MI FI
dt 2 dRI
E ({R}) y 0 H e ({R})y 0
y H e ({R})y down to the minimum
for each {R}
y H e ({R})y ???
dE ({R})
M I RI
dRI
{R} The Car-Parrinello algorithm
Car-Parrinello Molecular Dynamics
(i) integrate the equations of motion on the (long) time scale set by
the nuclear motion but nevertheless
Now, in classical mechanics the force on the nuclei is obtained from the
derivative of a Lagrangian with respect to the nuclear positions. This suggests
that a functional derivative with respect to the orbitals, which are interpreted as
classical fields, might yield the force on the orbitals, given a suitable Lagrangian.
In addition, possible constraints within the set of orbitals have to be imposed,
such as e.g.
orthonormality (or generalized orthonormality conditions that include an overlap
matrix).
Car-Parrinello Lagrangian
yyyy
y
Car and Parrinello (1985) have postulated the following Lagrangian
1 1
L
C
PM
R
2i
R
R
|
ii
2
i
E
{
D
F
T}
i
i
j
(
i
j
|
i i)
i
j
S LCP (t)dt
d dLCP (t) dLCP (t)
dt dR dR
d dLCP (t) dLCP (t)
dt dyi (r, t) dyi (r, t)
Car-Parrinello Equations of Motions
Car and Parrinello (1985) have derived equations of motions
E [
{y },{}
R ]
Z e2
M
RR D
FT
i
R
(,)
rt
|r
R
R()
t|
dr
y E [{yi},{}
R]
ijy
i rt
i(,) D
F
T
y
rt
j(,)
i(,)
rt j
H D
FTy rt
i(,) ijyj(,)
rt
j
E
phys
1
M R
R EDF
Ty
{}i
R2
E
con
s
1
MRR
1
y
i y
i| iE
DF
T[y
{}
i{
R}
] E
ph
ys
Tf
ict
R2 i 2
T
f
ict
1
y
ii|yi
i 2
Various Energies extracted from CPMD for a model system.
EDFT
Tfict
The fictitious kinetic energy of the electrons is found to perform bound oscillations
around a constant, i.e. the electrons do not heat up “ systematically “ in the presence
of the nuclei; note that Tfict is a measure for deviations from the exact Born-
Oppenheimer surface. Closer inspection shows actually two time scales of oscillations:
the one visible in the Figure stems from the drag exerted by the moving nuclei on the
electrons and is the mirror image of the EDFT fluctuations.
As a result the physical energy (the sum of the nuclear kinetic energy and the electronic
total energy which serves as the potential energy for the nuclei) is essentially constant
on the relevant energy and time scales.
Given the adiabatic separation and the stability of the propagation, the central
question remains if the forces acting on the nuclei are actually the “correct" ones
in Car-Parrinello molecular dynamics. As a reference serve the forces obtained
from full self-consistent minimizations of the electronic energy at each time step, i.e. Born-
Oppenheimer molecular dynamics with extremely well converged wavefunctions.
How to control adiabaticity?
Since the electronic degrees of freedom are described by much heavier masses
than the electronic masses, time step to perform CPMD simulations needs not to
be too small as compared to Ehrenfest molecular dynamics.
For a system with a gap in the spectrum, the lowest possible frequency of
“fictitious” electronic oscillations
2min ~ Egap
1/2
Egap
min ~
2 m ax ~ E cut
1/ 2
E
m ax ~ cut
1/ 2
t m ax ~
cut
E
y|H|y
c |H|c
n
m
n n m m
n 1
n
m
|c 2
|
Born-Oppenheimer Car-Parrinello
Born-Oppenheimer –versus- Car-Parrinello forces
Born-Oppenheimer –versus- Car-Parrinello: summary
from M Sprik
Ab-initio Molecular Dynamics: bibliography
• http://www.theochem.ruhr-uni-bochum.de/research/marx/cprev.en.html
•D G Kanhere
•Pune University
Lindemann Criteria
Mean Square Displacements
Extracting ionic density of
States
•Constant Temperature
•Constant Volume
•Phase space trajectories
•The Multiple Histogram Method
•To
•Extract Density of States
Sodium Clusters
● Simplest of atomic clusters
● Jellium model works ( Depends…)
● Nice delocalized charge density
● Magic Clusters at N=8,20,40,58,92,138,…
● Icosahedra for N=13,55,147,…
N=40 : peaked
N=50 : flat
Thermodynamics
Size sensitive specific heats
Magic melters
Higher than Bulk Melting
temperatures
The Case of Gallium and
Aluminum clusters
Ga12C is a Perfect
Icosahedra
Calculated Specific Heat Ga
Specific Heat