In:
Zeitschrift für Physikalische Chemie, Walter de Gruyter GmbH, Vol. 222, No. 1 ( 2008-1-1), p. 163-176
Abstract:
The potential energy surfaces and the spin–orbit couplings for states correlating with the lowest dissociation asymptote S 2 ( X 3 Σ - g ) + S - ( 2 P ) of the radical anion of thiozone have been calculated by full valence complete active space self-consistent field (CASSCF), internally contracted multi-reference configuration interaction (IC-MRCI) and for some of the states also by restricted coupled cluster with perturbative triples (RCCSD(T)) ab initio methods. For six electronic states lying below the electron detachment threshold: X 2 B 1 , A 2 B 2 , B 2 A 1 , C 2 A 2 , 4 Σ g - , and the second 2 A 1 , equilibrium geometries and harmonic wavenumbers are reported. For the ground state also anharmonic vibrational levels have been evaluated. Due to the intensity borrowing via vibronic coupling with the B 2 A 1 state also the dipole forbidden A – X transition becomes allowed in the Franck–Condon region of the UV spectrum. The C 2 A 2 state responsible for the blue color of ultramarine correlates adiabatically with the first dissociation asymptote S 2 ( X 3 Σ - g ) + S - ( 2 P ). Along the dissociation path the regions of vibronic and spin–orbit couplings were located. For the R S 2 - S larger than about 2.6Å the electron spin-states of the lowest dissociation asymptote are strongly mixed. The properties of the S 3 - electronic states are compared with those of O 3 - .
Type of Medium:
Online Resource
ISSN:
2196-7156
,
0942-9352
DOI:
10.1524/zpch.2008.222.1.163
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
2008
detail.hit.zdb_id:
201103-7
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