1

Chapter 2
Quantum chemistry using auxiliary
field Monte Carlo
1. The Hubbard-Stratonovich Transformation
2. Neuhausers shifted contour
3. Calculation of forces and PESs
4. Multireference AFMC
5. Examples of applications
2
Acknowledgment
z Shlomit Jacoby
z Prof. Daniel Neuhauser
z Prof. Anna Krylov
z Prof. Jan Martin
z Support:
Israel Science Foundation
Lise Meitner Center
3
Overview
z New quantum chemistry method:
Works in terms of basis sets
A continuous range of approximations from
Hartree-Fock to full CI
Based on Monte Carlo, but - No fixed nodes!
z Discuss the formalism
z Discuss application issues
z Show few results
4
Many-Fermion ground state
1
2

T T
H h V = +
(2
nd
quantization)
Electron density (matrix)
5
Goals
z Ground state energy
z Low lying excited states
z properties (correlation functions)
How to do that rigorously???
6
Boltzmann is Hot!
= + + +
1 0 1 0 2 2
a a a

H
e

0
0 0
E
a e
0
0 0
E
a e

1
1 1
E
a e

+
2
2 2
E
a e

+ +
0
H H
E He e

7
Groundstate is Cool
-108.55
-108.53
-108.51
-108.49
-108.47
-108.45
-108.43
-108.41
0 1 2 3 4 5
(au)
E
n
e
r
g
y

(
E
h
)
STO-3G
Full CI
( )

H
gs
H
He
E H E
e

= =

( ) ( )
( )
2

0
d
E H E
d

= <
HF Determinant
Variational!
8
How to do it???
( ) ( )

1 1
Slater Det.
New Slater Det.
T
h
N N
e

=
_
_
If electrons were non-interacting easy:
9
Proof (BCH)
( ) ( ) ( )

1 2

1 2 1 2
Slater Det.

1 2

1 2
Slater Det.
0
0
T T
T T T T T T
N
h h
N N
h h h h h h
N
d d d
N
e e c c c
e c e e c e e c e

_
( )
( )
( )

1

T T
N
h h h h
i j i j
ij ij
j j
e c e e c e



=
= =

10
2-body = very hard

1
huge # of det.
T
V
N
e

11
Slicing time
z Divide to N slices:
z Use
z Thus:
z Goal: Represent 2-body exponential as
sum of 1-body exponentials

1 2
H H H H
N
e e e e N



= = "

( )
1

2
2
T
T
V
H t
e e e O

= +
( )
1 1 1

2 2 2
1 2
T T T
T T T
V V V
H t t t
N
e e e e e e e O

= + "

12
Hubbard-Stratonovich Strategy
2 2
1 1
2 2 a
x
i
a
x
e e dx e

1 1
2 2
V V
V i
e e e d

x a V V = =
Fourier transform of a
Gaussian is a Gaussian:
An operator!
13
Problem in evaluation of integrals
z Consider a multidimensional integral
z Cant do on a grid! Why?
z Most points are on grid boundaries
( )
1
2
1
1
2
...
T
T
W
N
N
W
W
N
e f d
f
e d

1D
2:1
2D
8:1
3D
26:1
1D
2:2
2D
12:4
3D
56:8
14
Solution: Monte Carlo sampling
z The integral
z Is calculated by producing random
numbers that are Gaussian
distributed and summing
( )
1
2
1
1
2
...
T
T
W
N
N
W
W
N
e f d
f
e d

( )
1
...
N

( )
( )
1
1
...
...
N
N
W
f f



15
Monte Carlo scheme
( )
W
I
H
U e =

{ }
1
2
1
N
T
n n
n
V
W e

=


=
( )
( ) ( ) ( )
1 2

T T T
N
t iV t iV t iV
I
U e e e

+ + +
= "
G. Sugiyama and S. E. Koonin, Ann. Phys. N.Y. 168, 1 (1986).
16
Exercise
z A 1D particle is in a potential well V(x)
z Based on the Hubbard-Stratonovich
transformation derive a Monte Carlo
method to calculate its GS energy
z Hint:
( )
2
1

2
H p V x = +
( ) ( )
( )
2 2
2
1 1

2 2
1
2
p
i p
e x A e e x d
A e x d

=
=

17
Results for H
2
-2.50
-2.00
-1.50
-1.00
-0.50
0.00
0.50
1.00
0 2000 4000 6000
Iterations
C
o
r
r
e
l
a
t
i
o
n

e
n
e
r
g
y

(
e
V
)
=1 au
=2 au
=4 au
Sylvestrelli, Baroni
& Car PRL 71,
1148 1993
18
Whats causing the trouble?
( )
{ }

W
iV h H
T
e e
+
=

Noise (

)
Baer, Head-Gordon & Neuhauser, JCP 109, 6219 (1998)
Signal ()
1
V
T
Signal/Noise

0
( ) = O V i
W
T

1
19
Solution: contour-shift invariance
( )
W
H
U e

( ) ( ) ( ) i
( )
W
ia
d V i d V
H
U e e e
T T

=
0 0
2
1
Rom, Charutz & Neuhauser, CPL 270, 382 (1997)
20
Time slice stabilization
( ) ( )

=
H H
e e
( )
( ) ( )
( )
S i
e
V
K iV i
T
T

+
ln
`

S
= 0
{ } ( )

iS
e W D

21
The stabilizing shift
( )
( ) ( )
( ) ( ) 0

when , are very large:
( )
gs gs
=
Need to know exact GS density!
Use HF density as partial stabilizer
Baer, Head-Gordon & Neuhauser, JCP 109, 6219 (1998)
22
Successful Application to H
2
-1.05
-1.00
-0.95
-0.90
-0.85
0 2000 4000 6000
Iterations
C
o
r
r
e
l
a
t
i
o
n

e
n
e
r
g
y

(
e
V
)
= 1
au
= 2
au
= 4
au
= 8
au
( )
( )
E eV
E eV
corr
SC AFMC
corr
cc pVQZ

=
=
0 99 2
110
. ( )
.
1.4 au
23
Things to note
z No uncontrolled approximation is made
(no fixed nodes etc.)
z The auxiliary fields are sampled from a
universal distribution
{ }
( ) ( )

0
2
1
d V
T
e W
24
Some application issues
z Two codes:
Plane waves/pseudopotentials based code
Gaussian based code (Shlomit Jacoby):
Reads RHF/UHF GAMESS output
Can get data from CASSCF/GVB or spin flip
methods to perform multireference calculation
25
Inversion Barrier of Water
H
O
H
H
H
26
Tarczay et al
JCP 110, 11971
(1999)
Baer, CPL 324,
101 (1999)
-0.07
-0.06
-0.05
-0.04
-0.03
-0.02
-0.01
0
0.01
0 0.5 1 1.5 2
B
a
r
r
i
e
r

C
o
r
r
e
l
a
t
i
o
n

E
n
e
r
g
y

(
e
V
)
(au)
MP5
MP2
Inversion Barrier of Water
L=8 au
L=12 au
27
Electronic force on nuclei
( ) ( )
0
lim
R
E R R E R
dE
F
dR R

+
=
Force variance (statistical error) is infinite:
( )
( )
0
2
lim
R
E
F
R

= =
28
Solution: correlated sampling
z Auxiliary fields are sampled from a
universal Coulomb-Gauss distribution:
{ }
( ) ( )

0
2
1
d V
T
e W
z Straightforward correlated sampling:
Accurate potential surface
Geometries
Vibrational frequencies
29
Force variance is finite!
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0 0.5 1 1.5 2
dr=1e-3 au
dr=1e-4 au
dr=1e-5 au
S
t
.

D
e
v
.

F
o
r
c
e

(
a
u
)
(au)
30
N
2
: Bond length
1.05
1.06
1.07
1.08
1.09
1.1
1.11
0 0.5 1 1.5 2 2.5
R
e
(
A
)
(au)
Experiment
L=8 au
L=12 au
31
2100
2200
2300
2400
2500
2600
2700
2800
2900
0 0.5 1 1.5 2 2.5

e
(
c
m
-
1
)
(au)
Experiment
L=8 au
L=12 au
N
2
: Harmonic frequency
32
N
2
Heat of Formation
120
140
160
180
200
220
240
0 0.5 1 1.5 2 2.5
D
(
k
c
a
l
/
m
o
l
)
(au)
Experiment
L=8 au
L=12 au
33
The N
2
Potential Curve
Gdanitz CPL 283
253 (1998)
Baer, JCP 113,
473 (2000)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8 1.9 2 2.1 2.2 2.3 2.4
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y

(
e
V
)
R (au)
Hartree Fock
= 0.7 au
= 1.3 au
= 2.5 au
34
Multireference AFMC
'

' m m m
H
m
e S

=
'

'

m m m m
H
He H

=
= HC SCE

H
gs
n
n n
C e

( )
{ }

1 J = C H C C S C C
35
Singlet-Triplet Splitting of CH
2
5
10
15
20
25
30
0 0.5 1 1.5 2 2.5 3
J

(
k
c
a
l
/
m
o
l
e
)
(au)
1-singlet state
2-singlet states
36
(au)
0 1 2 3 4 5 6
E
(

)

-

E
F
C
I

(
E
h
)
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
= 1 au
= 0.5 au
= 0.2 au
= 0.1 au
= 0.01 au
H
2
ccp-VDZ
I=10
5
Sources of Error in AFMC
z > 0
zSE
z <
zAlso:
Basis-set
Frozen core
Rid of small
eigenvalues
of V
ijkl
37
Well-tempered AFMC
(au)
0 1 2 3 4 5 6 7 8
E
(

)

-

E
F
C
I



(
E
h
)
10
-4
10
-3
10
-2
10
-1
K = 1
K = 6
H
2
ccp-VDZ
I = 5x10
5

R
HH
= 1.2 A
zUsing several
determinants
considerably
improves the
performance
38
Simple example: excited states of H
2
Lines: FullCI
#Dets: 6
o = 0 au
o = 5 au
39
H
2
states: close up
40
Torsional Ethylene bond rapture
(deg)
0 20 40 60 80 100 120
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y

(
E
h
)
-78.2
-78.1
-78.0
-77.9
-77.8
= 0 (RHF)
= 0.1 au
= 0.5 au
= 1.0 au
= 2.0 au
= 3.0 au
= 4.5 au
C
2
H
4
6-31G
41
Singlet-Triplet states of Ethylene
Torsional angle (deg)
0 20 40 60 80 100 120
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y

(
e
V
)
0
1
2
3
4
5
6-31G
= 4.5 E
h
-1
1
1
A
g
1
3
B
1u
42
Single bond-breaking
HF H+F
Basis set: 6-31**
Full CI taken from Dutta and Sherrill,
J. Chem. Phys. 118, 1610 (2003).
-1
0
1
2
3
4
5
6
7
0 1 2 3 4
R (Angstrom)
E
n
e
r
g
y

a
b
o
v
e

m
i
n
.

(
e
V
)
FCI
b = 0.1 au
b = 1 au
b = 2 au
b = 3 au
b = 4 au
43
H
2
O PES for double bond breaking
AFMC results
at various
values of , vs.
Full-CI
R
eq
=0.96
0
2
4
6
8
10
12
14
0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3
R/Req
E
-
E
F
C
I
-
m
i
n

(
e
V
)
= 0
Full-CI
= 0.5 au
= 3 au
Basis set: DVZ
8 Detereminants
= 1.5 au
44
Summary
z New electronic structure method
z Formally exact, but has statistical error
z Can give PESs, break bonds, compute
excited states
z No fixed nodes approximation
z Balance mutireference and MC: method
to select a multi-reference space