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The document describes a complete basis set extrapolation scheme for CCSD(T) calculations. It presents formulas for extrapolating the Hartree-Fock and correlation energies to the complete basis set limit using 3-point and 2-point formulas. It then shows the formula used to estimate the complete basis set CCSD(T) energy by combining the extrapolated Hartree-Fock energy with extrapolated contributions from RI-MP2 and the difference between CCSD(T) and RI-MP2 energies.

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72 views2 pages

Notes

The document describes a complete basis set extrapolation scheme for CCSD(T) calculations. It presents formulas for extrapolating the Hartree-Fock and correlation energies to the complete basis set limit using 3-point and 2-point formulas. It then shows the formula used to estimate the complete basis set CCSD(T) energy by combining the extrapolated Hartree-Fock energy with extrapolated contributions from RI-MP2 and the difference between CCSD(T) and RI-MP2 energies.

Uploaded by

sahanchem
Copyright
© Attribution Non-Commercial (BY-NC)
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Complete Basis Set Extrapolation Scheme

January 27, 2010

CCSD(T)/CBS
The functional form adopted for the Hartree-Fock extrapolation1 is EHF (X) = EHF,lim + aebX , whereas that used to evaluate correlation energy limits,2 Ecorr (X) = Ecorr,lim + bX 3 . Three focal point extrapolation of Hartree-Fock complete basis set limit can be shown by EHF,lim =
2 EX E(X2) E(X1)

(1)

(2)

EX + E(X2) 2E(X1)

(3)

and two focal point extrapolation of correlation energy complete basis set limits can be shown by Ecorr,lim = X 3 Ecorr,X (X 1)3 Ecorr,X1 X 3 (X 1)3 (4)

Estimated Complete Basis Set Extrapolation Scheme for CCSD(T)


CBS,lim CBS,lim CBS,lim ECCSD(T) = EHF (D,T,Q) + ERI-MP2 (T,Q) + CCSD(T)CBS,lim(D,T)

(5)

where,
CBS,lim EHF (D,T,Q) = 2 EHF,Q EHF,D EHF,T EHF,Q + EHF,D 2EHF,T

(6)

CBS,lim ERI-MP2 (T,Q) =

43 Ecorr,Q 33 Ecorr,T 43 33

(7)

CCSD(T)CBS,lim (D,T) = CCSD(T)CBS,lim (D,T) RI-MP2CBS,lim (D,T) 1

(8)

References
[1] Feller, D. J. Chem. Phys. 1993, 98, 70597071. [2] Helgaker, T.; Klopper, W.; Koch, H.; Noga, J. J. Chem. Phys. 1997, 106, 96399646.

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