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Published September 6, 1990 | metadata_only
Journal Article

Singlet-triplet energy gaps in chlorine-substituted methylenes and silylenes


The singlet-triplet splittings of chlorine-substituted methylenes and silylenes have been studied by using the ab initio generalized valence bond (GVB) dissociation-consistent configuration interaction (DCCI) method. All chlorine-substituted methylenes and silylenes have singlet ground states, with calculated singlet-triplet splittings of 6.0, 20.5, 35.8, and 55.2 kcal/mo] for CHCl, CCl_2, SiHCl, and SiCl_2, respectively. We expect these results to be within 1 kcal/mo] of experiment. The DCCI result strongly suggests that the correct experimental singlet-triplet splitting of CHCl is 6.4 ± 0.7 kcal/mol. [Photoelectron studies of CHCl^- lead to either 11.4, 8.9, 6.4, 3.9, or 1.4 kcal/mo), depending on assignment.]

Additional Information

© 1990 American Chemical Society. Received: August 11, 1989; In Final Form: March 12, 1990. We acknowledge the support of the National Science Foundation under Grant Nos. CHE87-11567 (J.L.B.) and CHE83-18041 (W.A.G.).

Additional details

August 19, 2023
August 19, 2023