Ab initio and density functional theory calculations on heteroatom analogues of trimethylenemethane radical ions. Can a quartet be the ground state?

Journal of Physical Chemistry A

Volumn 106, Issue 12, 2002, Pages 2963-2969

  Brown, Eric C ^a   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

RADICAL IONS;

ALUMINA; ELECTRONS; GROUND STATE; PROBABILITY DENSITY FUNCTION;

ORGANIC COMPOUNDS;

EID: 0037188023     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp013905n     Document Type: Article

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38. . reaction.
39. y.
40. 3 would decrease. Therefore, with inclusion of overlap in the normalization, the weight of the first configuration in eqs 11 and 12 would be larger than the weight of the second configuration; and the combined weights of the last two configurations would have an intermediate value. Consequently, when overlap is significant, constraining the weights of the configurations in eqs 11 and 12 to be equal disadvantages these doublet wave functions, relative to the quartet, by making the doublets overall slightly antibonding, rather than nonbonding.
41. .- are allowed to pyramidalize, which lowers the energy of the radical anion by 0.4 kcal/mol, and gives EA = 5.7 kcal/mol.
42. s geometry with the two equivalent silyls pyramidalized in the opposite direction than the third. The energy of this doublet was computed to be 0.2 kcal/mol lower than that of the fully optimized quartet.
43. .+ was essentially unchanged.