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Excited electronic potential-energy surfaces and transition moments for the H3 system

Peng, Zhengwei and Kristyan, Sandor and Kuppermann, Aron and Wright, James S. (1995) Excited electronic potential-energy surfaces and transition moments for the H3 system. Physical Review A, 52 (2). pp. 1005-1023. ISSN 1050-2947. doi:10.1103/PhysRevA.52.1005.

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Four electronic states of H3 have been studied using a multiple-reference double-excitation configuration-interaction method with an extensive basis set of 75 Gaussian-type atomic orbitals. A total of 1340 ab initio points were calculated over a wide range of H3 molecular geometries. These four states include the ground state and the Rydberg 2s A12′ and 2pz A22″ states, as well as the state that in equilateral triangular geometry is related to the ground state by a conical intersection. Electric-dipole transition moments were also obtained between these states. The results show that the atomic and diatomic energetic asymptotes are accurately described. The barriers, wells, and energy differences also show good agreement compared to literature values, where available. The potential energies of the ground state and the 2pz A22″ Rydberg state display smooth and regular behavior and were fitted over the whole molecular geometries using a rotated Morse curve-cubic spline approach. The other two potential-energy surfaces reveal more complicated behaviors, such as avoided crossings, and will require a different fitting procedure to obtain global fitting. Finally, dynamical implications of these potential surfaces and electric-dipole transition moments are discussed.

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Additional Information:© 1995 The American Physical Society Received 30 January 1995 We acknowledge and thank the U. S. Air Force Astronautics Laboratory (Contract No. F04611-86-0016-67), the Department of Energy (Grant (DE-A03-83ER), and NSERC (Canada) for financial support. We also thank the NAS program of the NASA-Ames Research Center and the NSF-San Diego Supercomputer Center for use of their Cray Y-MP systems and the NASA Jet Propulsion Laboratory for use of their Cray X-MP and Y-MP computers, on which most of the calculations were done. Special thanks are due to Professor R. J. Buenker for supplying us with the Cray version of the MRD-CI code used in these calculations. Z.P. thanks Dr. Pablo Bruna for assistance.
Funding AgencyGrant Number
Air Force Astronautics LaboratoryF04611-86-0016-67
Department of Energy (DOE)(DE-A03-83ER
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
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Deposited On:23 Aug 2006
Last Modified:08 Nov 2021 20:17

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