AB INITIO CALCULATION OF $^{1.3}n\pi^{\ast}$ STATES IN CYCLOBUTANEDJONE

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 Title: AB INITIO CALCULATION OF $^{1.3}n\pi^{\ast}$ STATES IN CYCLOBUTANEDJONE Creators: Baiardo, Joseph; Vala, Martin Issue Date: 1981 Publisher: Ohio State University Abstract: Ab initio calculations at the RHF-SCF level have been curried out for the 4 vertical transitions to $^{1,3}n\pi^{*}$ states of cyclobutanedine (CBD) and $tetramethylcyclobutanedione^{1}$. In CBD localization of the $excitation^{2}$ (symmetry breaking) on one of the carbonyl groups occurs when the $D_{2}h$ symmetry restriction on the wavefunction is relaxed to $C_{s}$, keeping the nuclear framework in $D_{2}h$. This causes the vertical excitation energy to the first $^{1,3}n\pi^{*}$ $(A_{u})$ states to decrease form 6.08 and 5.87cv to 3.43and 3.09ev, respectively. Electron density distributions in these states $(A_{u})$ indicates that a distortion of the molecular framework form $D_{2}h$ in the ground state to $C_{2}v$ in the $^{1.3}n\pi^{*}$ $(A_{u})$ excited states is likely to occur. Description: 1. R. Spafford, J. Baiardo, J. Wrobel and M. Vala. J. Am. Chem. Soc., 98, 5217, 5225 (1976). 2. W.R. Wadt, W.A. Goddard, T.H. Dunning, J. Chem. Phys. 65, 438 (1976). H. Th. Jonkman et. al., proceedings of S.R.C. Atlas Symposium, No. 4, (1975). Author Institution: URI: http://hdl.handle.net/1811/11561 Other Identifiers: 1981-MH-1