IngentaConnect Ab initioRelativistic CI Calculations of the Spectroscopic Consta...

Authors: Khandogin Y.; Alekseyev A.B.; Liebermann H-P.; Hirsch G.; Buenker R.J.

Source: Journal of Molecular Spectroscopy, Volume 186, Number 1, November 1997 , pp. 22-33(12)

Abstract:

Spin-orbit MRD-CI calculations have been carried out for the potential energy surfaces of the seven lowest-lying electronic states of the BiOH molecule by employing relativistic effective core potentials. The HBiO isomer is found to be 4020 cm^-1less stable because of its inability to form multiple Bi–O bands. A bent³A Prime BiOH ground state is predicted, which is split into all three of its components by spin-orbit coupling. The calculatedX~₂A Prime –X~₁A prime splitting is computed to be 5217 cm^-1, but the correspondingX~₃–X~₂value is only 29 cm^-1. Finket al.have observed spectral bands which appear with aT_evalue of 6200 cm^-1which are likely caused by BiOH. Since calculations at the same level for BiF underestimate the observedX~₂–X~₁spin–orbit splitting by 650 cm^-1, it appears that the present calculations are consistent with this experimental assignment. A vibrational progression with a 500 cm^-1frequency is also observed and this result fits in well with the computed Bi–O stretch ohgr _evalue of 527 cm^-1. The calculations also find a relatively large¹ Dgr splitting (600 cm^-1) because of the bent BiOH geometry, with comparatively strong transitions to theX~₁A prime ground state, and it is suggested that the experimental BiOH assignment can be confirmed on this basis. Much stronger transitions to the¹ Dgr component should also be observed in emission in the 10 000 cm^-1range.Copyright 1997 Academic Press.

Language: English

Document Type: Research article

DOI: 10.1006/jmsp.1997.7423

Affiliations: Fachbereich 9—Theoretische Chemie, Bergische Universität–Gesamthochschule Wuppertal, Gaussstrasse 20, Wuppertal, D-42097, Germany:

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Ab initioRelativistic CI Calculations of the Spectroscopic Constants and Transition Probabilities for the Low-Lying States of the BiOH/HBiO Isomers