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Module-3: Ab Initio Molecular Dynamics

Car-Parrinello molecular dynamics (CPMD) is an ab initio molecular dynamics method that uses a fictitious kinetic energy term for molecular orbitals to propagate the electronic and nuclear degrees of freedom together in time. This allows for faster computation compared to traditional Born-Oppenheimer MD, which must optimize the electronic structure at each timestep. In CPMD, the electrons are kept "cold" while the nuclei are at a physical temperature through separate timescales. Proper choice of parameters like fictitious mass and timestep is needed to maintain adiabatic separation of the electronic and nuclear motion and conserve energy over the simulation.

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Anubhav Vardhan
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26 views

Module-3: Ab Initio Molecular Dynamics

Car-Parrinello molecular dynamics (CPMD) is an ab initio molecular dynamics method that uses a fictitious kinetic energy term for molecular orbitals to propagate the electronic and nuclear degrees of freedom together in time. This allows for faster computation compared to traditional Born-Oppenheimer MD, which must optimize the electronic structure at each timestep. In CPMD, the electrons are kept "cold" while the nuclei are at a physical temperature through separate timescales. Proper choice of parameters like fictitious mass and timestep is needed to maintain adiabatic separation of the electronic and nuclear motion and conserve energy over the simulation.

Uploaded by

Anubhav Vardhan
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Module-3

Ab Initio Molecular
Dynamics
April 01 & April 06

Ab Initio MD: BornOppenheimer MD


N
2
X
P
BOMD
I
H
({RI }, {PI }) =
+ Etot ({RI })
2MI
I=1

N
nD
2
X
PI
min
el
=
+
({ri }, {RI }) H
{ }
2MI
I=1

({ri }, {RI })

Eo

N
X
ZI ZJ
+
RIJ
J>I

rR I

el | | = rR |H
el | | +
|H
I
D
E
el | |
6=
|rRI H

el | | +
|rRI H

el |rR |
|H
I

Basis set should be large enough!


Convergence of wave function and energy conservation:
Time
CPU time (s)
Converge conservatio
step
for 1 ps
nce (a.u.) n (a.u./ps)
(fs)
trajectory
0.25

10-6

10-6

16590

10-6

10-6

4130

10-6

6 x 10-6

2250

10-4

1 x 10-3

1060

Concerns:
Wavefunction optimisation at every MD step is time consuming!
Note: wfn has to be well converged.

Car-Parrinello MD

Basic Idea:
Timescale separation: Electronic part is fast
Nuclear part is slow
Classical mechanical adiabatic energy-scale
separation
making 2 classical subsystems
that are adiabatically energyscale separated.
1.
2.

nuclear coordinates
orbital coefficients

Lagrangian:

LCP =

X1

Note:

MI R I +

el
H

N,
LCP LCP (RN , R

i| i

+ constraints
n

, n)

is the molecular orbital (spatial)


X
ci
i =

is the Slater det.

is the fictitious mass for orbitals

LCP

LCP (R , R ,
N

, )

Equations of motion can be computed as


d
L
D
=
dt
i

d @L
@L
=
I
dt @ R
@RI

FI =

i i =

@
@RI

h i|

Hel

Hel

h i|

@
+
(constraints)
@RI

h i|

(constraints)

Within the KS theory constraints are due to orthonormality of orbitals:

XX
i

ij (h i |

ji

ij )

Nuclear temperature
(physical temperature):

T /

Fictitious temperature: T orb. /

MI R I

X
i

i| i

No energy transfer between physical system and the


orbital (quasi-adiabatic separation of dynamics)
Orbitals should move close to the corresponding Bornorb
Oppenheimer solutions: T has to be small enough
(close to zero K cold electrons)
Energy transfer from hot nuclei to cold electrons
should be strictly avoided during the dynamics

No overlap in the vibrational density of states


(orbital motion has to be much above 4000 cm-1)
Thus motion can be kept adiabatically separable!
Energy is well
conserved (no
noise due to
SCF procedure!)

Thus, motion about the actual BO surface


High freq. oscillations are not relevant in the
timescale of the nuclear dynamics: thus not
only averages, but also time-dependent
properties can also be computed

Time step should be small (to sample high


freq. motion of orbital degrees of freedom):
usually about 0.06-0.12 fs
(Very small) Fictitious mass should be
appropriately chosen (400-700 au)
Energy conservation can be checked to verify
the accuracy of dynamics.

CP/10 a.u. /
CP/5 a.u. /
BO/10 a.u. /10-6
BO/100 a.u. /10-6
BO/100 a.u. /10-5

BO/100 a.u. /10-4

Computationally efficient
Better energy conserving
Not truly an BO MD; dynamics could get
affected if parameters are not chosen
properly.
Small tilmestep (~1/10 smaller)
Adiabatic separation doesnt work in
some cases (zero band gap)
Better wfn extrapolation algorithms are
available today; thus wfns can be
converged fast, and BOMD can be made
computationally efficient!

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