Introduction to Electronic Structure Simulations. Exercises.

1
Exercise 9 - derivation The Car-Parrinello method.
The best strategy to gure out if everything is right with the exercise paper is to derive all key
equations ourselves. For the sake of simplicity let us consider a case, where only the lowest eigenvalue
has to be calculated. The result will be easily extendable to a more complicated problem, where
several lowest eigenvalues are to be obtained. In the course of theoretical mechanics, the Lagrangian
is dened as a dierence of the kinetic and potential energies
L = T U (1)
. After T and U are expressed explicitly, one obtains
L =

2

C
2
m

mn
C
m
H
mn
C
n
. (2)
This equation can be rewritten in the following form:
L =

2

C
2
m

mn
C
m
H
mn
C
n

mn
C
m
S
mn
C
n

mn

. (3)
The extra term on the right hand side obviously does not ruin equality, and it will help to maintain
generality in later steps. The equation of motion
d
dt
L

C
k
=
L
C
k
(4)
reads as

C
n
= 2

m
C
m
(H
mn
+ S
mn
) . (5)
In order to obtain this expression, one calculates the derivatives as follows:
d
dt
L

C
k
=

C
k
(6)
and
L
C
k
=

mn
(C
m

nk
+ C
n

mk
) H
mn

mn
(C
m

nk
+ C
n

mk
) S
mn
. (7)
In eq.(7), symmetry properties of matrices H and S can be used, then simplifying the expression
and combining it with eq. (6) leads to eq. (5).
The Lagrange factor is obtained from the equillibrim condition. If

C
n
= 0, eq. (5) transforms
into

m
H
mn
C
m
=

m
S
mn
C
m
, (8)
Introduction to Electronic Structure Simulations. Exercises. 2
which is nothing dierent than the Schrodinger equation in the matrix representation. The eigenvalue
is equal to the negative of the total energy that can be calculated as the expectation value
=

mn
C
n
H
mn
C
m
. (9)
After this result is inserted in eq.(5), we arrive at the equation

C
n
= 2

m
C
m
(H
mn
S
mn
) . (10)
This equation describes an evolution that does not have to end up in the equilibrium. But one can
assist with that by adding a friction term and transforming eq.(10) into form

C
n
= F
n

C
n
, (11)
with F
n
being the right-hand side of eq.(10). This equation can be solved numerically, if the deriva-
tives are expressed as nite dierences as follows:

C
n
(t + h/2) =
C
n
(t + h) C
n
(t)
h
, (12)

C
n
(t) =

C
n
(t + h/2)

C
n
(t h/2)
h
=
C
n
(t + h) + C
n
(t h) 2C
n
(t)
h
2
, (13)

C
n
(t) =
C
n
(t + h) C
n
(t h)
2h
. (14)
Eqs. (12-14) can be inserted into eq. (10), which leads us to result

+
h
2

C
n
(t + h) = 2C
n
(t)

h
2

C
n
(t) + h
2
F
n
(15)
that can be used for implementing the Verlet algorithm.