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Multiconfigurational perturbation theory

with separately scaled energy terms
Péter Nagy and Ágnes Szabados
Laboratory of Theoretical Chemistry, Eötvös University,Budapest, Hungary
nagy0peter@gmail.com
Short content Introduction
• Feenberg-scaling in perturbation theory (PT) A widely applied approach in quantum chemistry to obtain wavefunctions and energies is perturbation theory (PT). There exist numerous
• Grimme-scaling in Møller-Plesset PT multireference function based formulations which provide perturbative corrections. Multiconfigurational PT (MCPT) is one of these[1].
To improve the second order Møller-Plesset PT a special scaling philosophy was introduced by Grimme [4] in the single-reference frame-
• Multiconfigurational PT (MCPT)
work. This scaling is based on the systematic separation of the different contributions of doubly excited states. It was shown[2] that a similar
• Grimme-scaling as a two parameter Feenberg-scaling scaling can be obtained by a system-dependent optimization procedure, as suggested by Feenberg[3].
• Extension of the theories to MCPT In this work scaling methods are investigated within MCPT, following the ideas of Feenberg and Grimme. We introduce various novel scaling
• Results and conclusion strategies suited for covalent bond dissociation. The basic theory of the applied methods and pilot applications on small model systems are
presented.

Feenberg-scaling in PT Multiconfigurational PT Generalized Feenberg scaling
• Initial partition: Ĥ = Ĥ (0) + Ŵ • Reference function: Ψ0
(0)
= c0|0i +
model space
P
ck |ki • Partitioning: Ĥ = Ĥ (0)′(p) + Ŵ ′(p)
1 µ  
k6=0 ∂
E (2)(p) + E (3)(p) = 0
• Repartition: Ĥ = Ĥ (0) + Ŵ − Ĥ (0) µ ∈ ℜ • Determine (p) from (1): ∂p (2)
|1 − µ
{z } | 1 {z
−µ } |0i: principal determinant, |ki: excited determinant
• Separate the energy into terms BG and AG,H: B and A:
Ĥ (0)′ Ŵ ′ • Bi-orthogonal basis set in the CI space:
3 (0)
groups
P in G
P groups
P
∂ P
• Determine µ from: ∂µ E (i)′ = 0 (1) |Ψ0 i and |ki ; k = 0, . . . , NF CI E (2)(p) = pG bk = pGBG
i=0 (0) G k G

(2) 2 hΨ̃0 | = c10 h0| and hk̃| = hk| − cck0 h0| groups
P P in H
in G P
(E ) E (3)(p) =
• The new energy: E (2)′ = E (2)−E (3) and E (3)′ = 0 pGpH akl =
• Bi-orthogonal MCPT formulae (definition of b and a): G,H k6=0 l6=0
Grimme’s spin-component scaling (SCS) (2)
1,2×
P (0)
1 h0|Ŵ |kihk̃|Ŵ |Ψ0 i P
groups
P
(pGpH(AGH + AHG) − δGHpGBG)
EMCPT = − c0 ∆k = bk
• Separate doubles: parallel (’triplet’, |Tk i = b+ + − −
σ aσ iσ jσ |0i) k6=0 k6=0
G,H

+ − − • Substitution to (2): A p = B provide the paramerters
and anti-parallel (’singlet’, e.g. |Sk i = b+σ σ iσ jσ |0i)
a (3)
1,2×
P 1−4×
P h0|Ŵ |kihk̃|Ŵ |lihl̃|Ŵ |Ψ0 i
(0) P
EMCPT = c0∆l ∆k = akl
k6=0 l6=0 k,l6=0
• Singles (L) , triples and quadruples (J) also appear, Specification of the partitioning
at difference with ordinary MP2 and MP3
• (Møller–Plesset: nondiagonal H (0) in MRPT)
• Grouping variants:
• (Epstein-Nesbet: degeneracy leads often to divergence)
◦ S(TLJ): two groups, S and the others, two optimized param.
• Davidson-Kapuy:
|0i |Sk i |Tki ◦ Opt-Fee: one group, no separation, one optimized param.
• System independent scaling parameters: pS = 1.2; pT = 13 ◦ Grimme: scaling the S and T groups with Grimme‘s param. ∆DK DK DK
k = Ek − E0 = hk|F̂ |ki − h0|F̂ |0i

2× 2× ◦ STLJ: four groups, four optimized param. • Denominator as a difference of IPs and EAs [5]:
(2) P |h0|H|Tk i|2 P |h0|H|Sk i|2
ESCS-MP2 = −pT − pS occ. virt.
∆k ∆k
ǫ⊕
P P
Tk Sk ∆IP/EA
k = i − ǫ⊖
a
i i
Parameters pS and pT can be determined following Feenberg, (0) (0) (0) (0)
hΨ0 |Ĥ|Ψ0 i hΨ |a+Ĥa |Ψ i
ǫ⊕
i = − 0 (0) i + i (0)0 (ǫ⊖
a analogously)
but the concept of two parameters requires generalization. Averaging method (0) (0)
hΨ0 |Ψ0 i hΨ0 |ai ai|Ψ0 i
• Averaging before determining the scaling factors,
• sum for certain principals, |ki in the model space
• weight them with their importance:
model
Pspace
c2k BGk
kP
BGAV = c2k
and analogusly for AAV
GH
Scaling in SR case Scaling in DK partitioning
Bond fission of HF molecule, 3−21G basis, IP/EA partitioning Bond fission of HF molecule, 3−21G basis

0.1
CAS 2x2 ref. 0.005
0.08 SRPT2
SRPT3 0.012
Consequences
∆E = EPT−EFCI / a. u.

∆E = EPT−EFCI / a. u.

S(TLJ)−SRPT3 0.009 0
0.06 Opt−Fee−SRPT3
Grimme−SRPT2 0.006
MCPT3 • Essential, non-obvious factors: the partitioning,
0.04 0.003 the grouping strategy and the choice of the princi- −0.005
0 pal determinant MCPT2
MCPT3
0.02 −0.003 S(TLJ)−MCPT3
0.8 1 1.2 1.4 Summary −0.01 Opt−Fee−MCPT3
Grimme−MCPT2
0 STLJ−MCPT3
• Feenberg-scaling is generalizable for the MR case
1 2 3 4 5 6 • We explored several partitionings, grouping vari- 1 2 3 4 5 6
Bond length / Å Bond length / Å
ants and we averaged for principal determinants
• Scaled SRPT does not compete with MCPT upon dissociation • Some scaling variants ameliorate MCPT, e.g. Opt–Fee, Grimme
• There are cases where scaling may provide better
results • Grouping matters a lot (especially scaling of non-doubles)

Further plans
Scaling in IP/EA partitioning • Find a generally applicable scaling strategy Scaling, averaging and damping
Bond fission of HF molecule, 3−21G basis • Reduce the calculation cost by finding Grimme- Bond fission of HF molecule, 3−21G basis
type system independent scaling parameters 0.01
AV−MCPT3
0.006 AV−S(TLJ)−MCPT3
AV−Opt−Fee−MC
0.008 AV−STLJ−MCPT3
0.004 References NONAV−MCPT3
∆E = EPT−EFCI / a. u.

∆E = EPT−EFCI / a. u.

NONAV−S(TLJ)−MCPT3
NONAV−STLJ−MCPT3
0.002 0.006
[1] Á. Szabados, Z. Rolik, G. Tóth, and P. R.
0 Surján. J. Chem. Phys., 122, 114104, (2005).
MCPT2 0.004
MCPT3 [2] Á. Szabados. J. Chem. Phys., 125, 214105,
−0.002 S(TLJ)−MCPT3
Opt−Fee−MCPT3
(2006).
−0.004 Grimme−MCPT2 [3] E. Feenberg. Phys. Rev., 103, 1116, (1956). 0.002
STLJ−MCPT3
for comparison: DK−MCPT3
−0.006
[4] S. Grimme. J. Chem. Phys., 118, 9095, (2003).
0
1 2 3 4 5 6 [5] A. Zaitsevskii, JP. Malrieu. Chem. Phys. Lett., 1 2 3 4 5 6
Bond length / Å 223, 597, (1995). Bond length / Å
• IP/EA denominators remove irregular behaviour at large distance • Averaging and damping improves parallelity
• Scaling may improve MCPT, but the grouping is still an issue