Explicitly correlated coupled cluster methods with pair-specific geminals

Hans Joachim Werner; Gerald Knizia; Frederick R. Manby

doi:10.1080/00268976.2010.526641

Explicitly correlated coupled cluster methods with pair-specific geminals

Hans Joachim Werner
, Gerald Knizia
, Frederick R. Manby

Chemistry

Research output: Contribution to journal › Article › peer-review

216 Scopus citations

Abstract

Explicitly correlated MP2-F12 and CCSD(T)-F12 methods with orbital-pair-specific Slater-type geminals are proposed. The fixed amplitude ansatz of Ten-no is used, and different exponents of the Slater geminal functions can be chosen for core-core, core-valence, and valence-valence pairs. This takes care of the different sizes of the correlation hole and leads to improved results when inner-shell orbitals are correlated. The complications and the extra computational cost as compared to corresponding calculations with a single geminal are minor. The improved accuracy of the method is demonstrated for spectroscopic properties of Br₂, As₂, Ga₂, Cu₂, GaCl, CuCl, and CuBr, where the d-orbitals are treated as core.

Original language	English (US)
Pages (from-to)	407-417
Number of pages	11
Journal	Molecular Physics
Volume	109
Issue number	3
DOIs	https://doi.org/10.1080/00268976.2010.526641
State	Published - Feb 10 2011

All Science Journal Classification (ASJC) codes

Biophysics
Molecular Biology
Condensed Matter Physics
Physical and Theoretical Chemistry

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10.1080/00268976.2010.526641

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title = "Explicitly correlated coupled cluster methods with pair-specific geminals",

abstract = "Explicitly correlated MP2-F12 and CCSD(T)-F12 methods with orbital-pair-specific Slater-type geminals are proposed. The fixed amplitude ansatz of Ten-no is used, and different exponents of the Slater geminal functions can be chosen for core-core, core-valence, and valence-valence pairs. This takes care of the different sizes of the correlation hole and leads to improved results when inner-shell orbitals are correlated. The complications and the extra computational cost as compared to corresponding calculations with a single geminal are minor. The improved accuracy of the method is demonstrated for spectroscopic properties of Br2, As2, Ga2, Cu2, GaCl, CuCl, and CuBr, where the d-orbitals are treated as core.",

author = "Werner, \{Hans Joachim\} and Gerald Knizia and Manby, \{Frederick R.\}",

note = "Funding Information: This work was funded by the DFG as part of a NSF-DFG grant and by the Stuttgart SimTech Cluster of Excellence. HJW also acknowledges generous support from the Fonds der Chemischen Industrie. We are grateful to Kirk Peterson and Grant Hill for providing their new basis sets prior to publication and for many helpful discussions. HJW thanks C. H{\"a}ttig and D. Tew for providing test results for their (F12*) method, which were very useful for debugging our implementation.",

year = "2011",

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doi = "10.1080/00268976.2010.526641",

language = "English (US)",

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pages = "407--417",

journal = "Molecular Physics",

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TY - JOUR

T1 - Explicitly correlated coupled cluster methods with pair-specific geminals

AU - Werner, Hans Joachim

AU - Knizia, Gerald

AU - Manby, Frederick R.

N1 - Funding Information: This work was funded by the DFG as part of a NSF-DFG grant and by the Stuttgart SimTech Cluster of Excellence. HJW also acknowledges generous support from the Fonds der Chemischen Industrie. We are grateful to Kirk Peterson and Grant Hill for providing their new basis sets prior to publication and for many helpful discussions. HJW thanks C. Hättig and D. Tew for providing test results for their (F12*) method, which were very useful for debugging our implementation.

PY - 2011/2/10

Y1 - 2011/2/10

N2 - Explicitly correlated MP2-F12 and CCSD(T)-F12 methods with orbital-pair-specific Slater-type geminals are proposed. The fixed amplitude ansatz of Ten-no is used, and different exponents of the Slater geminal functions can be chosen for core-core, core-valence, and valence-valence pairs. This takes care of the different sizes of the correlation hole and leads to improved results when inner-shell orbitals are correlated. The complications and the extra computational cost as compared to corresponding calculations with a single geminal are minor. The improved accuracy of the method is demonstrated for spectroscopic properties of Br2, As2, Ga2, Cu2, GaCl, CuCl, and CuBr, where the d-orbitals are treated as core.

AB - Explicitly correlated MP2-F12 and CCSD(T)-F12 methods with orbital-pair-specific Slater-type geminals are proposed. The fixed amplitude ansatz of Ten-no is used, and different exponents of the Slater geminal functions can be chosen for core-core, core-valence, and valence-valence pairs. This takes care of the different sizes of the correlation hole and leads to improved results when inner-shell orbitals are correlated. The complications and the extra computational cost as compared to corresponding calculations with a single geminal are minor. The improved accuracy of the method is demonstrated for spectroscopic properties of Br2, As2, Ga2, Cu2, GaCl, CuCl, and CuBr, where the d-orbitals are treated as core.

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UR - https://www.scopus.com/pages/publications/79951746307#tab=citedBy

U2 - 10.1080/00268976.2010.526641

DO - 10.1080/00268976.2010.526641

M3 - Article

AN - SCOPUS:79951746307

SN - 0026-8976

VL - 109

SP - 407

EP - 417

JO - Molecular Physics

JF - Molecular Physics

IS - 3

ER -

Explicitly correlated coupled cluster methods with pair-specific geminals

Abstract

All Science Journal Classification (ASJC) codes

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