multiply charged ions quantum chemical computations trento, may 2002 lecture 2
DESCRIPTION
Basis Sets - 2 l=m=n=o ‘s’ l or m or n = 1‘p’ l + m + n = 2‘d’ l + m + n = 3‘f’TRANSCRIPT
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Multiply Charged IonsQuantum Chemical ComputationsTrento, May 2002Lecture 2
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Basis Sets - 1
basn
jjiji rcr
1
2
A
A
Rr
Rr
iqr
Ne
Ne
Ne
Usually atom-centered
N
iii rcr
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Basis Sets - 2 2
,,, rnml ezyxrzyx l=m=n=o ‘s’
l or m or n = 1 ‘p’l + m + n = 2 ‘d’l + m + n = 3 ‘f’
63.typ
iiprimitiveicontracted c
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Types of Basis Set• Minimal (one s, p (& d, f) function per shell.
STO-3G• Double- (two functions per shell or valence
shell). E.g. 3-21G, 6-31G, DZ, SV, …• Triple-, Quadruple-• Polarisation functions:
Poor Overlap
+ =
Better Overlap
Double- + polarisation (e.g. 6-31G*, 6-31G**, cc-pVDZ, SVP) usually adequate for HF, geometry.
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Dynamic Correlation
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CorrelationN
e e e
e
Nas likely as
N
e e
mixed with
He [1s2]
N
e
e
He [2p2]
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Configuration Interaction
... ,
, , ,
,
, ,
,
,00CI
virtocc
virtoccvirtocc
nn
ai bj ck
abcijkijkabc
nn
ai bj
abijijab
nn
ai
aiia
c
ccc
kjiHF 0
kjaai
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CI
• Only CISD practical (partly physically motivated!!)
• Slow convergence with basis set size (roughly 1/n3)
• Size inconsistent
H
H
H
H
al.et H ai0 H
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MPn
nnnn
n
n
xxx
xxxxxx
nx
21
22221
11211
HF1
• Approximate solution to correct Schrödinger equation
• Exact solution to a different equation where Vee is replaced by <Vee>
•Apply perturbation theory (Møller-Plesset)•To second order (MP2), gives most of the
correlation energy in favourable cases
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MP2
occ virtn
ji
n
ba
2
biai2
baji
ajbjMPE
• Poor performance of MP2 when small band gap
• Size consistent
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Coupled Clusters
... ,
, , ,
,
, ,
,
,00exact
virtocc
virtoccvirtocc
nn
ai bj ck
abcijkijkabc
nn
ai bj
abijijab
nn
ai
aiia
c
ccc
0ˆ
exact Te
321
32ˆ
ˆˆˆ1 ˆ
ˆ21ˆ
21ˆ1
TTTT
TTTeT
virtocc nn
ai
aiiatT
,
,01
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CC 32ˆ ˆ21ˆ
21ˆ1 TTTeT
41
212
22134
31123
2121
ˆ
ˆ241ˆˆ
21ˆ
21ˆˆˆ
ˆ21ˆˆˆˆ
21ˆˆ1
TTTTTTT
TTTTTTTeT
21ˆˆ1 ˆ TTTSD Restrict to T2 (CCSD):
0ˆ
CCSD SDTe
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CCSD(T) et al.
41
212
22
3112
2121
ˆ
ˆ241ˆˆ
21ˆ
21
ˆ21ˆˆˆ
21ˆˆ1
TTTT
TTTTTTe SDT
• Only CCSD, CCSD(T) generally feasible• Size consistent• CCSD(T) very accurate where band gap is
large (“method of choice”)
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Basis Sets and CorrelationSlow convergence with basis size!
N
e e
mixed with
He [1s2]
N
e
e
He [2p2]
3max
,,1l
EE exactcorrelcalccorrel
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Correlation Consistent B.S.s
• cc-pVDZ: 3s, 2p, 1d (lmax = 2)• cc-pVTZ: 4s, 3p, 2d, 1f (lmax = 3)• cc-pVQZ: 5s, 4p, 3d, 2f, 1g (lmax = 4)• cc-pV5Z: 6s, 5p, 4d, 3f, 2g, 1h (lmax = 5)
T. H. Dunning et al.:
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Extrapolation
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Basis Set Dependence
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Other ExtrapolationHF/STO-3G HF/DZ limite HF
MP2
CCSD
Full-CI exact result
Larger Basis Set
BetterDescription of
electronicCorrelation
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G2, G3, etc.HF/STO-3G HF/DZ limite HF
MP2
CCSD
Full-CI exact result
Larger Basis Set
BetterDescription of
electronicCorrelation
• •
•
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G2
EG2 = EQCISD(T)(6-311G**) + E(MP4, diffuse) + E(MP4, 3df) + …