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) |
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Pages (from-to) | 7-14 |
Number of pages | 8 |
Journal | Chemical Physics Letters |
Volume | 260 |
Issue number | 1-2 |
DOIs | |
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.