A theoretical study of the lowest 2 B 1, 2 A 1 and 2 B 2 electronic states in H2S+ and a comparison with corresponding states in related systems |
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| Authors: | Pablo J Bruna Gerhard Hirsch Miljenko Perić Sigrid D Peyerimhoff Robert J Buenker |
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| Institution: | 1. Lehrstuhl für Theoretische Chemie , Universit?t Bonn , Wegelerstra?e 12, D-5300, Bonn 1, West Germany;2. Lehrstuhl für Theoretische Chemie , Universit?t Bonn , Wegelerstra?e 12, D-5300, Bonn 1, West Germany;3. Institut za Fizi?ku Hemiju, Prirodno-Matemati?kog Fakulteta , Studentski Trg 12, 11000, Beograd, Jugoslavia;4. Lehrstuhl für Theoretische Chemie , Gesamthochschule Wuppertal , Gau?stra?e 20, D-5600, Wuppertal 1, West Germany |
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| Abstract: | Large scale configuration interaction calculations are employed to study the potential energy surfaces of the three lowest lying states in H2S+. The calculated structural data for the X 2 B 1 and A 2 A 1 states are in very good agreement with previous evidence, but the 2 B 2 state is found to exhibit an S---H2]+ structure with large SH bond separations and a very small internuclear angle of 32°. Energies and wavefunctions are calculated for all three vibrational modes in the X 2 B 1 and A 2 A 1 excited states of H2S+ and D2S+ and the corresponding Franck-Condon factors for the A 2 A 1-X 2 B 1 band are determined; a maximum in absorption intensity is predicted to occur for v′2 = 5–6 in H2S+ and for v′2 = 7–8 in D2S+ for the A 2 A 1-X 2 B 1 transition, for which the calculated T 0 energy of 18 620 cm-1 is in excellent agreement with the experimentally determined value of 18 520 cm-1. Extensive comparison is made with the other AH2 systems PH2, NH2 and H2O+ and trends with respect to geometry, vertical excitation and ionization energies as well as vibrational structure are pointed out; for this purpose the 2 B 2 potential energy curve of PH2 has also been calculated. |
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