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

✍ Scribed by Z. Peng; Aron Kuppermann; James S. Wright

• Publisher: Elsevier Science
• Year: 1990
• Tongue: English
• Weight: 616 KB
• Volume: 175
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(90)85550-v

✦ Synopsis

Four electronic states of H3 have been studied using a multi-reference configuration interaction method and a basis set of AOs. The calculations were carried out at a fixed bond angle of 60". The four states include the ground state and the Rydberg 2s and 2p, states, as well as the state which in the equilateral triangular geometry is related to the ground state by a conical intersection. Electric dipole transition moments were calculated between all of these states at every geometry. The potential energies obtained for the various states show that the atomic and diatomic asymptotes are accurately described, and that the barriers, wells and energy differences also show good agreement compared to literature values, where available. The ground state and 2p, Rydberg state potential energy surfaces were fitted over the whole geometric configuration space spanned using a rotated Morse curvecubic spline approach, and show smooth contour maps appropriate for studies in excited-state reaction dynamics. ' Work performed in partial fulfillment of the requirements for the Ph.D. Degree in Physics at the California Institute of Technology. * Contribution No. 8183.