Rovibronic Levels for the (1–3)3Πg Manifold of B2: Exterior Complex Scaling Finite Element Calculations Based on an Adiabatic and a Strictly Diabatic Basis
✍ Scribed by S. Andersson; L.A. Pederson; N. Elander
- Publisher
- Elsevier Science
- Year
- 2002
- Tongue
- English
- Weight
- 244 KB
- Volume
- 214
- Category
- Article
- ISSN
- 0022-2852
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✦ Synopsis
A one-dimensional complex scaled finite element method was applied on an adiabatic basis of B 2 in order to find rovibronic term energy values for the (1) 3 g ; (v, N ) = (0-8, 0-25) and (2) 3 g ; (v, N ) = (0-10, 0-25) levels. The method was also applied to the (1) 3 g ; (v, N ) = (0-8, 0-25) and (2) 3 g ; (v, N ) = (0-1, 0-25) levels in a strictly diabatic framework. Adiabatic single-channel and diabatic coupled-channel total wavefunctions were obtained and used in order to identify the vibrational levels. Comparing levels for the interacting two-state (1-2) 3 g and three-state (1-3) 3 g system, a constant energy shift of about 1.7 cm -1 is found. Comparisons between the adiabatic Born-Oppenheimer (BO) and the diabatic (1) 3 g ; (v, N ) = (0-8, 0-25) levels show differences between -20 and 7 cm -1 , while the corresponding shifts for the (2) 3 g ; (v, N ) = (0, 0-25) and (1, 0-25) levels are about 50 and 60 cm -1 , respectively. A comparison between our three-state approximation and experimental observations of the (2) 3 g -A 3 u electronic transition shows a difference in the line positions of about 665 cm -1 . The calculated widths for all but the (1) 3 g ; (v, N ) = (7-8, 0-25), as well as the (2) 3 g ; (v, N ) = (0, 0-25) BO and diabatic rovibronic levels, have small but with N increasing predissociation rates. The (1) 3 g ; (v > 8, N = 0-25) BO and the (2) 3 g ; (v, N ) = (1, 0-25) diabatic levels are strongly predissociated with widths ≥16 cm -1 .