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Simplified methods for ab initio calculations. The valence states of CH2 and CH 2+

par Gervy Decoster, Christine ;Verhaegen, Georges
Référence International journal of quantum chemistry, 12, 1, page (115-131)
Publication Publié, 1977

Article révisé par les pairs

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Résumé :

Three simplifying methodds are discussed and applied to the four lowest valence states of CH2(3B1, 1A1, 1B1 and 1Σ g+(1A 1*)) and to the two lowest of CH 2+(2A1 and 2∏u(2B1)). These methods concern: (1) the development of polarization functions for Gaussian‐lobe basis sets by least‐square fitting of numebrical multiconfigurational atomic fuinctions (this approach is tested also on (C2H2, (2) the use of intermediate Hamiltonians to calculate avoided crossings between potential hypersurfaces, and (3) thecalculation of correlation energies using an atoms‐in‐molecule approach. The calculated equilibrium geometries of the CH2 States are within 0.02 Å and 5° of available experimental data. The calculated term values and ionization potentials, Te(1A1 = 0.35 eV, Te (1B1) = 1.22 eV, Te (1Σ g+(1A 1*)) 2.48 eV, I.P. (2A1) = 10.39 eV and I. P. (2∏u(2B1)) = 10.58 eV, are in agreement with some recent theoretical studies, and are very close to existing experimental information. Copyright © 1977 John Wiley & Sons, Inc.