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Keld L. Bak

First-order nonadiabatic coupling matrix elements from multiconfigurational self-consistent-field response theory

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First-order nonadiabatic coupling matrix elements from multiconfigurational self-consistent-field response theory. / Bak, Keld Lars; Jørgensen, Poul; Jensen, Hans Jørgen Aa; Olsen, Jeppe; Helgaker, Trygve.

In: The Journal of Chemical Physics, Vol. 97, No. 10, 1992, p. 7573-7584.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

Harvard

Bak, KL, Jørgensen, P, Jensen, HJA, Olsen, J & Helgaker, T 1992, 'First-order nonadiabatic coupling matrix elements from multiconfigurational self-consistent-field response theory', The Journal of Chemical Physics, vol. 97, no. 10, pp. 7573-7584.

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Author

Bak, Keld Lars ; Jørgensen, Poul ; Jensen, Hans Jørgen Aa ; Olsen, Jeppe ; Helgaker, Trygve. / First-order nonadiabatic coupling matrix elements from multiconfigurational self-consistent-field response theory. In: The Journal of Chemical Physics. 1992 ; Vol. 97, No. 10. pp. 7573-7584.

Bibtex

@article{3c224c67f4154dc093321c8493d016e5,
title = "First-order nonadiabatic coupling matrix elements from multiconfigurational self-consistent-field response theory",
abstract = "A new scheme for obtaining first-order nonadiabatic coupling matrix elements (FO-NACME) for multiconfigurational self-consistent-field (MCSCF) wave functions is presented. The FO-NACME are evaluated from residues of linear response functions. The residues involve the geometrical response of a reference MCSCF wave function and the excitation vectors of response theory. Advantages of the method are that the reference state is fully optimized and that the excited states, represented by the excitation vectors, are strictly orthogonal to each other and to the reference state. In a single calculation the FO-NACME between the reference state and several excited states may be obtained simultaneously. The method is most well suited to describe situations where the dominant configurations for the two states differ mainly by a single electron replacement. When the dominant configurations differ by two electrons many correlating orbitals are required in the MCSCF reference state calculation to accurately describe the FO-NACME. FO-NACME between various states of H 2, MgH2, and BH are presented. These calculations show that the method is capable of giving quantitatively correct results that converge to the full configuration interaction limit. Comparisons are made with state-averaged MCSCF results for MgH2 and finite-difference configuration interaction by perturbation with multi-configurational zeroth-order wave function reflected by interactive process (CIPSI) results for BH.",
author = "Bak, {Keld Lars} and Poul J{\o}rgensen and Jensen, {Hans J{\o}rgen Aa} and Jeppe Olsen and Trygve Helgaker",
year = "1992",
language = "English",
volume = "97",
pages = "7573--7584",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "AMER INST PHYSICS",
number = "10",

}

RIS

TY - JOUR

T1 - First-order nonadiabatic coupling matrix elements from multiconfigurational self-consistent-field response theory

AU - Bak, Keld Lars

AU - Jørgensen, Poul

AU - Jensen, Hans Jørgen Aa

AU - Olsen, Jeppe

AU - Helgaker, Trygve

PY - 1992

Y1 - 1992

N2 - A new scheme for obtaining first-order nonadiabatic coupling matrix elements (FO-NACME) for multiconfigurational self-consistent-field (MCSCF) wave functions is presented. The FO-NACME are evaluated from residues of linear response functions. The residues involve the geometrical response of a reference MCSCF wave function and the excitation vectors of response theory. Advantages of the method are that the reference state is fully optimized and that the excited states, represented by the excitation vectors, are strictly orthogonal to each other and to the reference state. In a single calculation the FO-NACME between the reference state and several excited states may be obtained simultaneously. The method is most well suited to describe situations where the dominant configurations for the two states differ mainly by a single electron replacement. When the dominant configurations differ by two electrons many correlating orbitals are required in the MCSCF reference state calculation to accurately describe the FO-NACME. FO-NACME between various states of H 2, MgH2, and BH are presented. These calculations show that the method is capable of giving quantitatively correct results that converge to the full configuration interaction limit. Comparisons are made with state-averaged MCSCF results for MgH2 and finite-difference configuration interaction by perturbation with multi-configurational zeroth-order wave function reflected by interactive process (CIPSI) results for BH.

AB - A new scheme for obtaining first-order nonadiabatic coupling matrix elements (FO-NACME) for multiconfigurational self-consistent-field (MCSCF) wave functions is presented. The FO-NACME are evaluated from residues of linear response functions. The residues involve the geometrical response of a reference MCSCF wave function and the excitation vectors of response theory. Advantages of the method are that the reference state is fully optimized and that the excited states, represented by the excitation vectors, are strictly orthogonal to each other and to the reference state. In a single calculation the FO-NACME between the reference state and several excited states may be obtained simultaneously. The method is most well suited to describe situations where the dominant configurations for the two states differ mainly by a single electron replacement. When the dominant configurations differ by two electrons many correlating orbitals are required in the MCSCF reference state calculation to accurately describe the FO-NACME. FO-NACME between various states of H 2, MgH2, and BH are presented. These calculations show that the method is capable of giving quantitatively correct results that converge to the full configuration interaction limit. Comparisons are made with state-averaged MCSCF results for MgH2 and finite-difference configuration interaction by perturbation with multi-configurational zeroth-order wave function reflected by interactive process (CIPSI) results for BH.

UR - http://www.scopus.com/inward/record.url?scp=0001544994&partnerID=8YFLogxK

M3 - Journal article

AN - SCOPUS:0001544994

VL - 97

SP - 7573

EP - 7584

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 10

ER -