Refinements in the vibration frequencies of H3 and D3
| Autor: | Carney, G. D. |
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| Zdroj: | Molecular Physics; March 1980, Vol. 39 Issue: 4 p923-933, 11p |
| Abstrakt: | Refinements in vibration intervals of the order of 1 per cent are reported for H3+ and D3+. 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 H3+ agree to within 0·01 Å; refined fundamental frequencies are vA = 3220·48 and vE = 2545·99 cm-1 for H3+, and vA = 2332·94 and vE = 1848·12 cm-1 for D3+. Einstein coefficients for spontaneous emission of radiation from infrared active states of H3+ and D3+ 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 H3+. |
| Databáze: | Supplemental Index |
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