Multireference Configuration Interaction and Second-Order Perturbation Theory Calculations for the 1³A'', 1¹A'', and 1¹A' Electronic States of Vinylnitrene and Vinylphosphinidene

Parasuk, V.; Cramer, C. J.
Chem. Phys. Lett. 1996, 260, 7.

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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