Ab initio predictions of the zero field splittings and the singlet-triplet transition strengths for the n → π transition of selenoformaldehyde

The energy levels of the lower valence and Rydberg states of selenoformaldehyde, CH 2 Se, have been calculated by the SCF/CI method. Wavefunctions for the ROHF (restricted open shell Hartree-Fock) states were obtained with the Binnings-Curtis double-ζ basis set, augmented with Rydberg and polarizati...

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Bibliographic Details
Published in:Canadian journal of chemistry 1993-10, Vol.71 (10), p.1706-1712
Main Authors: Moule, D.C, Chantranupong, L, Judge, R.H, Clouthier, D.J
Format: Article
Language:English
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Summary:The energy levels of the lower valence and Rydberg states of selenoformaldehyde, CH 2 Se, have been calculated by the SCF/CI method. Wavefunctions for the ROHF (restricted open shell Hartree-Fock) states were obtained with the Binnings-Curtis double-ζ basis set, augmented with Rydberg and polarization functions. Configuration interaction was applied to the parent configurations, PCMO (parent configuration molecular orbital). Oscillator strengths were evaluated for the allowed electric dipole transitions by the RPA (random phase approximation), and SOPPA (second-order polarization propagator approximation) methods. The spin-orbit contribution to the zero field splitting of the first triplet state, 3 A 2 (n,π*) as well as the oscillator strengths to the three spin components were calculated by perturbation theory. These calculations predict that the S x , S y , and S z components are shifted by −96.091,−96.707, and + 29.167 cm −1 , respectively, from their unperturbed position. The oscillator strengths for the three components f x , f y , and f z of the 3 A 2 (n,π*) ←  1 A 1 (g.s.) transition were calculated to be 3.45 × 10 −7 , 1.15 × 10 −7 , and 173.0 × 10 −7 .
ISSN:0008-4042
1480-3291
DOI:10.1139/v93-212