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Excited States And Photochemistry Of Saturated Molecules. Vii. Potential Energy Surfaces In Excited Singlet States Of Methane, Mark S. Gordon, James W. Caldwell

Mark S. Gordon

Potential energy surfaces are investigated for a number of low‐lying excited singlet states of methane, using a split valence plus Rydberg basis set and singly excited CI. Of the six minima found, the lowest two are valence states. The lowest minimum corresponds to the products 1 1 B 1 CH2+1 1Σ g + H2, in agreement with the observed threshold photochemistry, and is accessible by five separate routes from the lowest vertical state. The second valence minimum is a square planar structure. Of the four Rydberg minima detected, one is a local minimum on the otherwise dissociative B 1surface and …