Multireference configuration interaction and second-order perturbation theory calculations for the 1 3A″, 1 1A″, and 1 1A′ electronic states of vinylnitrene and vinylphosphinidene

Vudhichai Parasuk; Christopher J. Cramer

doi:10.1016/0009-2614(96)00865-2

Multireference configuration interaction and second-order perturbation theory calculations for the 1 ³A″, 1 ¹A″, and 1 ¹A′ electronic states of vinylnitrene and vinylphosphinidene

Vudhichai Parasuk
, Christopher J. Cramer

Administration (RIO)

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

28 Scopus citations

Abstract

MRCI and CASPT2 calculations from a (4, 4) MCSCF active space predict both vinylnitrene and vinylphosphinidene to have ³A″ ground states. For vinylnitrene, the lowest open-shell singlet (¹A″) and closed-shell singlet (¹A′) states lie 15 and 40 kcal/mol higher in energy, respectively. The corresponding relative singlet energies in vinylphosphinidene are 17 and 23 kcal/mol, respectively. The reduced separation between the singlet states in H₂C=CHP compared to H₂C=CHN is attributed to decreased conjugation between the double bond and the pnictogen atom in the phosphinidene.

Original language	English (US)
Pages (from-to)	7-14
Number of pages	8
Journal	Chemical Physics Letters
Volume	260
Issue number	1-2
DOIs	https://doi.org/10.1016/0009-2614(96)00865-2
State	Published - Sep 20 1996

Bibliographical note

Funding Information:
We are grateful for high-performance vector and parallel computing resources made available by the Minnesota Supercomputer Institute and the University of Minnesota-IBM Shared Research Project, respectively, and to the NSF for support (CHE-9525819). We also thank Chulalongkorn University for making resources available for VP to make an extended visit to the University of Minnesota. Finally, it is a pleasure to acknowledge stimulating discussions with Drs. T. Bally, W. Borden, R. McMahon, R. Squires, and P. Wenthold.

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10.1016/0009-2614(96)00865-2

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@article{684584a8ff4246b88c12ebc64b3224eb,

title = "Multireference configuration interaction and second-order perturbation theory calculations for the 1 3A″, 1 1A″, and 1 1A′ electronic states of vinylnitrene and vinylphosphinidene",

abstract = "MRCI and CASPT2 calculations from a (4, 4) MCSCF active space predict both vinylnitrene and vinylphosphinidene to have 3A″ ground states. For vinylnitrene, the lowest open-shell singlet (1A″) and closed-shell singlet (1A′) states lie 15 and 40 kcal/mol higher in energy, respectively. The corresponding relative singlet energies in vinylphosphinidene are 17 and 23 kcal/mol, respectively. The reduced separation between the singlet states in H2C=CHP compared to H2C=CHN is attributed to decreased conjugation between the double bond and the pnictogen atom in the phosphinidene.",

author = "Vudhichai Parasuk and Cramer, \{Christopher J.\}",

note = "Funding Information: We are grateful for high-performance vector and parallel computing resources made available by the Minnesota Supercomputer Institute and the University of Minnesota-IBM Shared Research Project, respectively, and to the NSF for support (CHE-9525819). We also thank Chulalongkorn University for making resources available for VP to make an extended visit to the University of Minnesota. Finally, it is a pleasure to acknowledge stimulating discussions with Drs. T. Bally, W. Borden, R. McMahon, R. Squires, and P. Wenthold.",

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doi = "10.1016/0009-2614(96)00865-2",

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T1 - Multireference configuration interaction and second-order perturbation theory calculations for the 1 3A″, 1 1A″, and 1 1A′ electronic states of vinylnitrene and vinylphosphinidene

AU - Parasuk, Vudhichai

AU - Cramer, Christopher J.

N1 - Funding Information: We are grateful for high-performance vector and parallel computing resources made available by the Minnesota Supercomputer Institute and the University of Minnesota-IBM Shared Research Project, respectively, and to the NSF for support (CHE-9525819). We also thank Chulalongkorn University for making resources available for VP to make an extended visit to the University of Minnesota. Finally, it is a pleasure to acknowledge stimulating discussions with Drs. T. Bally, W. Borden, R. McMahon, R. Squires, and P. Wenthold.

PY - 1996/9/20

Y1 - 1996/9/20

N2 - MRCI and CASPT2 calculations from a (4, 4) MCSCF active space predict both vinylnitrene and vinylphosphinidene to have 3A″ ground states. For vinylnitrene, the lowest open-shell singlet (1A″) and closed-shell singlet (1A′) states lie 15 and 40 kcal/mol higher in energy, respectively. The corresponding relative singlet energies in vinylphosphinidene are 17 and 23 kcal/mol, respectively. The reduced separation between the singlet states in H2C=CHP compared to H2C=CHN is attributed to decreased conjugation between the double bond and the pnictogen atom in the phosphinidene.

AB - MRCI and CASPT2 calculations from a (4, 4) MCSCF active space predict both vinylnitrene and vinylphosphinidene to have 3A″ ground states. For vinylnitrene, the lowest open-shell singlet (1A″) and closed-shell singlet (1A′) states lie 15 and 40 kcal/mol higher in energy, respectively. The corresponding relative singlet energies in vinylphosphinidene are 17 and 23 kcal/mol, respectively. The reduced separation between the singlet states in H2C=CHP compared to H2C=CHN is attributed to decreased conjugation between the double bond and the pnictogen atom in the phosphinidene.

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