Refinements in the vibration frequencies of H 3 + and D 3 +

Author: Carney G.D.  

Publisher: Taylor & Francis Ltd

ISSN: 1362-3028

Source: Molecular Physics, Vol.39, Iss.4, 1980-03, pp. : 923-933

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Abstract

Refinements in vibration intervals of the order of 1 per cent are reported for H 3 + and D 3 + . These improved intervals result from the addition of polarization terms to the electronic wavefunction previously obtained with a complete configuration-interaction treatment of electron correlation using a 21 floating gaussian lobe basis. Twelve additional floating gaussian lobe orbitals were used to construct 78 additional configuration-interaction functions. Positions and exponents of these additional floating gaussian lobe orbitals were carefully chosen to allow for polarization of the correlated wavefunctions. Calculated vibrational state-averaged and observed geometries for H 3 + agree to within 0·01 Å; refined fundamental frequencies are v A = 3220·48 and v E = 2545·99 cm -1 for H 3 + , and v A = 2332·94 and v E = 1848·12 cm -1 for D 3 + . Einstein coefficients for spontaneous emission of radiation from infrared active states of H 3 + and D 3 + are reported, and an alternative to the Carney-Porter method of vibration analysis is used to confirm the accuracy of their method for axial molecules such as H 3 + .