Direct construction of diabatic states in the CASSCF approach. Application to the conical intersection of the 1A2 and 1B1 excited states of ozone

W. Domcke; C. Woywod

doi:10.1016/0009-2614(93)90110-M

Direct construction of diabatic states in the CASSCF approach. Application to the conical intersection of the ¹A₂ and ¹B₁ excited states of ozone

W. Domcke, C. Woywod

TUM Emeriti of Excellence

Technical University of Munich

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

150 Scopus citations

Abstract

A generally applicable scheme for the construction of diabatic electronic wavefunctions in the CASSCF/MRCI approach is proposed. It is noted that the redundancy of variational parameters in the CASSCF wavefunction can be exploited to define daibatic molecular orbitals. A maximum-overlap criterion at neighbouring nuclear goemetries is employed. In a second step. diabatic N-electron wavefunctions which retain as much as possible their configurational character are constructed by blocked-diagonalization of the Hamiltonian matrix. The procedure is illustrated to the ¹A₂-¹B₁ conical intersection in ozone.

Original language	English
Pages (from-to)	362-368
Number of pages	7
Journal	Chemical Physics Letters
Volume	216
Issue number	3-6
DOIs	https://doi.org/10.1016/0009-2614(93)90110-M
State	Published - 31 Dec 1993

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title = "Direct construction of diabatic states in the CASSCF approach. Application to the conical intersection of the 1A2 and 1B1 excited states of ozone",

abstract = "A generally applicable scheme for the construction of diabatic electronic wavefunctions in the CASSCF/MRCI approach is proposed. It is noted that the redundancy of variational parameters in the CASSCF wavefunction can be exploited to define daibatic molecular orbitals. A maximum-overlap criterion at neighbouring nuclear goemetries is employed. In a second step. diabatic N-electron wavefunctions which retain as much as possible their configurational character are constructed by blocked-diagonalization of the Hamiltonian matrix. The procedure is illustrated to the 1A2-1B1 conical intersection in ozone.",

author = "W. Domcke and C. Woywod",

note = "Funding Information: This work has been supported by the Deutsche Forschungsgemeinschafta nd the Fonds der Chem-ischen Industrie. The authorsw ould like to thank Dr. A.L. Sobolewski for stimulating discussions and Professor B.O. Roos for making the MOLCAS-2 package available.",

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T1 - Direct construction of diabatic states in the CASSCF approach. Application to the conical intersection of the 1A2 and 1B1 excited states of ozone

AU - Domcke, W.

AU - Woywod, C.

N1 - Funding Information: This work has been supported by the Deutsche Forschungsgemeinschafta nd the Fonds der Chem-ischen Industrie. The authorsw ould like to thank Dr. A.L. Sobolewski for stimulating discussions and Professor B.O. Roos for making the MOLCAS-2 package available.

PY - 1993/12/31

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N2 - A generally applicable scheme for the construction of diabatic electronic wavefunctions in the CASSCF/MRCI approach is proposed. It is noted that the redundancy of variational parameters in the CASSCF wavefunction can be exploited to define daibatic molecular orbitals. A maximum-overlap criterion at neighbouring nuclear goemetries is employed. In a second step. diabatic N-electron wavefunctions which retain as much as possible their configurational character are constructed by blocked-diagonalization of the Hamiltonian matrix. The procedure is illustrated to the 1A2-1B1 conical intersection in ozone.

AB - A generally applicable scheme for the construction of diabatic electronic wavefunctions in the CASSCF/MRCI approach is proposed. It is noted that the redundancy of variational parameters in the CASSCF wavefunction can be exploited to define daibatic molecular orbitals. A maximum-overlap criterion at neighbouring nuclear goemetries is employed. In a second step. diabatic N-electron wavefunctions which retain as much as possible their configurational character are constructed by blocked-diagonalization of the Hamiltonian matrix. The procedure is illustrated to the 1A2-1B1 conical intersection in ozone.

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Direct construction of diabatic states in the CASSCF approach. Application to the conical intersection of the ¹A₂ and ¹B₁ excited states of ozone

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