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Analysis and predictions of the vibronic spectrum of the ethynyl radical C2H by ab initio methods

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Zeitschrift für Physik D Atoms, Molecules and Clusters

Abstract

A purely ab initio study of the vibronic structure of the C2H spectrum in the region up to 7000 cm−1, which is complicated by the coupling of theX 2Σ+ andA 2 II systems, is presented. The potential surfaces for the three lowest-lying electronic states 12 A′, 22 A′ and 12 A″ correlating withX 2Σ+ andA 2 II at the linear molecular geometry are calculated for the various geometrical distortions by means of the multireference configuration interaction (MRD-CI) method. These adiabatic surfaces are transformed into suitable diabatic counterparts. An approach is developed for a simultaneous treatment of three electronic states coupled via the bending and C-C stretching vibrations. Spin-orbit splitting of the vibronic levels and the vibronically averaged values for the hyperfine coupling constants are computed. The results obtained in this study enable a reliable explanation of the available experimental findings of the C2H spectrum and predict a number of features to be verified by future experiments.

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Authors and Affiliations

  1. Faculty of Science, Institute of Physical Chemistry, University of Belgrade, Studentski trg 16, POB 550, 11001, Beograd, Yugoslavia

    M. Perić

  2. Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, W-5300, Bonn 1, Federal Republic of Germany

    S. D. Peyerimhoff

  3. Lehrstuhl für Theoretische Chemie, Bergische Universität-Gesamthochschule Wuppertal, Gausstrasse 20, W-5600, Wuppertal 1, Federal Republic of Germany

    R. J. Buenker

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Perić, M., Peyerimhoff, S.D. & Buenker, R.J. Analysis and predictions of the vibronic spectrum of the ethynyl radical C2H by ab initio methods. Z Phys D - Atoms, Molecules and Clusters 24, 177–198 (1992). https://doi.org/10.1007/BF01426704

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