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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
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 …
Excited States And Photochemistry Of Saturated Molecules. Ix. Vertical Excited States Of Silane, Mark S. Gordon
Excited States And Photochemistry Of Saturated Molecules. Ix. Vertical Excited States Of Silane, Mark S. Gordon
Mark S. Gordon
The vertical excited states of silane are investigated using ten different basis sets to systematically compare the effects of (a) Rydberg functions, (b) diffuse d functions, (c) valence d functions, and (d) a split valence shell. Wavefunctions are generated using all singly excited configurations, excluding inner shells. The low‐lying singlet states are dominated by excitations into the diffuse orbitals, while low‐lying triplets have significant valence character. Valence d functions have a minor effect on excitation energies if an adequate valence s p basis set is used. The main effect of Rydbergd functions is to introduce additional Rydberg states below the …