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Trygve Helgaker
Centre for Theoretical and Computational Chemistry
Department of Chemistry, University of Oslo, Norway
1 / 24
Introduction
I Requirements for correlated and uncorrelated wave-function models are different
Overview
1
conventional CI
explicitly correlated R12-CI
the Hylleraas function
basis-set extrapolation
Overview
2 / 24
Eloc = (H)/
1
2
2
1
1
+
H = 21 22
2
2
r1
r2
r12
I
200
100
!100
!0.5
0.0
0.5
0.5
1.0
0.0
3 / 24
I The helium wave function with one electron fixed at a separation of 0.5a0 from the nucleus
I
total wave function with the corresponding HartreeFock wave function subtracted
0.5
0.0
- 0.5
0.00
- 0.05
- 0.10
- 1.0
- 0.5
0.0
0.5
1.0
4 / 24
Cusp conditions
I Consider the helium Hamiltonian expressed in terms of r1 , r2 , and r12 :
H=
2
1X
2 i=1
2
2
2Z
+
+
ri2
ri ri
ri
2
2
1
+
2
r12
r12 r12
r12
+
2Z
2
+
ri ri
ri
=0
= Z (ri = 0)
ri ri =0
1
= (r12 = 0)
r12 r12 =0
2
ri =0
1
2
r12 r12
ri
=0
r12 =0
0.4
0.1
!1.0
!0.5
0.5
1.0
5 / 24
we must model the hole accurately for chemical accuracy in our calculations
I We shall compare the convergence of the following expansions for the helium ground-state
1
conventional CI
I single-zeta STOs
I numerical orbitals
CI with a correlating function
I CI-R12
the Hylleraas function
0.4
0.1
!1.0
!0.5
0.5
1.0
6 / 24
I The helium ground-state FCI wave function constructed from such STOs becomes:
P`0 (cos 12 )
`
I
X
n1 n2
`
4 X
(1)m Y`,m (1 , 1 )Y`,m (2 , 2 )
2` + 1 `
7 / 24
N=1:
1 = |1s 2 |
N=2:
100
150
200
250
10-2
-4
10
single- CI
numerical CI
I The use of fully numerical orbitals reduces the error by a few factors
I
8 / 24
Correlating functions
I By introducing
2 r2 r2
r12
1
2
2r1 r2
we may write the FCI wave function in the form
X
2k
FCI (r1 , r2 , r12 ) = exp [ (r1 + r2 )]
cijk r1i r2j + r2i r1j r12
cos 12 =
ijk
I Since only even powers of r12 are included, the cusp condition can never be satisfied
CI
=0
r12 r12 =0
I However, if we include a term linear in r12
CI
r12 =
1
1 + r12 CI
2
I We may always satisfy the cusp condition by multiplication with a correlating function:
=1+
Trygve Helgaker (CTCC, University of Oslo)
1
2
X
i>j
rij
9 / 24
100
150
200
250
10-2
10-4
single- CI
numerical CI
10-6
single- CI-R12
10 / 24
k
cijk r1i r2j + r2i r1j r12
ijk
t = r1 r2 ,
s = r1 + r2 ,
u = r12
I Only even powers in t are needed for the singlet ground state:
cijk s i t 2j u k
ijk
100
150
200
250
10-2
10-4
10-6
10-8
single- CI
numerical CI
single- CI-R12
Hylleraas
11 / 24
Convergence rates
I We have seen the reason for the slow convergence of FCI wave functions
DZ
-90
90
QZ
TZ
-90
90
-90
5Z
90
-90
90
I Let us now examine the rate of convergence for the helium atom using the
1
2
partial-wave expansion
principal expansion
4f
1s
4f
5f
6f
3d
4d
3d 4d 5d 6d
2p
3p
4p
2p 3p 4p 5p 6p
2s
3s
4s
1s 2s 3s 4s 5s 6s
principal expansion
Trygve Helgaker (CTCC, University of Oslo)
partial-wave expansion
12 / 24
CI
L =
L
X
`=0
I
1s2s,
2s 2 ,
1s3s,
3s3s,
3s 2 , . . .
EL = EL EL1 = 0.074226 L +
1 4
2
0.030989 L +
1 5
2
13 / 24
1 :
1s 2
2 : 1s 2 , 1s2s, 2s 2 , 2p 2
I The principal expansion is higher in energy at each truncation level (Eh ):
L
0
1
2
3
EL
2.879
2.901
2.903
2.904
N
1
2
3
4
EN
2.862
2.898
2.902
2.903
I However, the asymptotic convergence rate of the energy corrections is the same
EN = EN EN1 = c4 N
1 4
2
14 / 24
En`m = an6
En`m = 90 a = 1.08a
n`m
E` = a (2` + 1)
n6 a (2` + 1)
n6 dn
`+1/2
n=`+1
= 15 a(2` + 1) ` +
1 5
2
= 52 a ` +
1 4
2
EL = EL E = 52 a
`+
1 4
2
+ 52 a
`=L+1
`+
L+1/2
1 4
2
d` =
2
a (L
15
+ 1)3
En = an2 n6 = an4
I The asymptotic truncation error of principal expansion with n N is therefore
EN = EN E = a
X
n=N+1
n4 a
N+1/2
n4 dn = 13 a(N + 21 )3
I The two series converge slowly but smoothly and may therefore be extrapolated
Trygve Helgaker (CTCC, University of Oslo)
15 / 24
Some observations
I The number of AOs at truncation level N in the principal expansion is given by
Nao =
N
X
n2 = 61 N(N + 1)(N + 2) N 3
i=1
I The dependence of the error in the correlation energy on the CPU time is thus:
EN T 1/4
I Each new digit in the energy therefore costs 10000 times more CPU time!
1 minute
1 week
200 years
16 / 24
Overview
1
basis-set extrapolation
17 / 24
-25.0
HF
core
-0.050
FCI HallL
valence
-25.2
FCI HfcL
-0.150
I The valence correlation energy can be recovered with smaller basis sets
18 / 24
1s
2s
2p
3s
3p
3d
4s
4p
4d
4f
5s
5p
5d
5f
5g
I The occupation numbers provide a natural criterion for selecting basis functions:
1l
2l
3l
4l
5l
s
2.000000
1.924675
0.008356
0.000347
0.000021
0.674781
0.004136
0.000331
0.000034
0.008834
0.000124
0.000016
0.000186
0.000011
0.000018
19 / 24
cc-pVX Z,
cc-pVDZ
+3s3p3d
3s2p1d
cc-pVTZ
+4s4p4d4f
4s3p2d1f
cc-pVQZ
+5s5p5d5f 5g
5s4p3d2f 1g
number of AOs
X2
X3
NX = 31 (X + 1)(X + 3/2)(X + 2)
I The proportion of the correlation energy recovered increases slowly:
X
%
2
67
3
88
4
95
5
97
6
98
I Extensions:
aug-cc-pVX Z,
cc-pCVX Z,
aug-cc-pCVX Z
20 / 24
1
1
1
1
I cc-pVTZ: 4s3p2d1f
2
1
1
1
1
1
1
I cc-pVQZ: 5s4p3d2f1g
2
1
1
5
f
1
1
1
1
21 / 24
X
cc-pVDZ
numerical
2
77.1
85.6
3
93.0
95.6
4
97.3
98.0
5
98.7
98.9
I The Coulomb hole calculated with standard cc-pVX Z and numerical orbitals:
0.28
0.28
0.19
-
-2
0.19
2
-2
0.28
-2
0.28
0.19
-
0.19
2
-2
22 / 24
all
basis set
6-31G
6-31G
6-311G
cc-pVDZ
cc-pVTZ
cc-pVQZ
cc-pV5Z
cc-pV6Z
extrapolated
R12
cc-pCVDZ
cc-pCVTZ
cc-pCVQZ
cc-pCV5Z
cc-pCV6Z
extrapolated
R12
Ne MP2
113.4
150.3
209.0
185.5
264.3
293.6
306.2
311.8
319.5
320(1)
228.3
329.1
361.5
374.1
379.8
387.6
388(1)
Ne CCSD
114.3
152.2
210.6
189.0
266.3
294.7
305.5
309.9
315.9
316(1)
232.2
331.4
362.7
373.7
378.2
384.4
384(1)
N2 MP2
236.4
305.3
326.4
306.3
373.7
398.8
409.1
413.8
420.3
421(2)
382.7
477.8
510.7
523.1
528.7
536.4
537(2)
N2 CCSD
225.8
308.3
326.3
309.3
371.9
393.1
400.6
403.7
408.0
408(2)
387.8
478.2
507.1
516.7
520.6
526.0
526(2)
H2 O MP2
127.8
194.6
217.4
201.6
261.5
282.8
291.5
295.2
300.3
300(1)
241.3
317.5
342.6
352.3
356.4
362.0
361(1)
H2 O CCSD
134.4
203.8
224.9
211.2
267.4
286.0
292.4
294.9
298.3
298(1)
251.8
324.2
346.5
353.9
356.9
361.0
361(2)
I Some observations:
I
I
I
I
23 / 24
Extrapolations
I Correlation-consistent basis sets are realizations of the principal expansion
I The error in the energy is equal to the contributions from all omitted shells:
EX
n=X +1
n4 X 3
E =EX + AX 3
E =EY + AY 3
we eliminate A to obtain the following two-point extrapolation formula:
E =
X 3 EX Y 3 EY
X3 Y 3
I Mean absolute error in the electronic energy of CH2 , H2 O, HF, N2 , CO, Ne, and F2 :
mEh
plain
extr.
DZ
194.8
TZ
62.2
21.4
QZ
23.1
1.4
5Z
10.6
0.4
6Z
6.6
0.5
R12
1.4
kJ/mol
plain
extr.
DZ
73.5
TZ
28.3
18.5
QZ
11.4
0.7
5Z
6.0
0.0
6Z
3.5
0.0
I Chemical accuracy is now achieved with just 168 AOs (QZ), at a fraction of the cost
Trygve Helgaker (CTCC, University of Oslo)
Basis-set extrapolation
24 / 24