The electronic spectrum of SiH4: Jahn-Teller Rydberg series

Velasco, A. M.; Lavín, C.; Sánchez de Merás, A. M. J.; Sánchez Marín, J.

doi:doi:10.1063/1.3664629

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Vibrational frequencies and spectroscopic constants from quartic force fields for cis-HOCO: The radical and the anion

The use of accurate quartic force fields together with vibrational configuration interaction recently predicted gas phase fundamental vibrational frequencies of the trans-HOCO radical to within 4 cm−1 of experimental results for the two highest frequency modes. Utilizing the same approach, we are providing a full list of fundamental vibrational frequencies and spectroscopic constants for the cis-HOCO system in both radical and anionic forms. Our predicted geometrical parameters of the cis-HOCO r...

Confirmed assignments of isomeric dimethylbenzyl radicals generated by corona discharge

The controversial vibronic assignments of isomeric dimethylbenzyl radicals were clearly resolved by using different precursors. By employing corresponding dimethylbenzyl chlorides as precursors, we identified the origins of the vibronic bands of the dimethylbenzyl radicals generated by corona discharge of 1,2,4-trimethylbenzene. From the analysis of the spectra observed from the dimethylbenzyl chlorides in a corona excited supersonic expansion, we revised previous assignments of the 3,4-, 2,4-, ...

The aim of the present theoretical work is to provide data necessary for a better understanding of the electronic spectrum of the silane molecule, which is affected by the Jahn-Teller effect. By selecting an adequate distorted C_2v geometry of SiH₄, the three lower Koopmans ionization potentials are evaluated with the equation of motion coupled cluster of singles and doubles method. Vertical excitation energies for the different Rydberg series converging to the three Jahn-Teller components are inferred from ab initio coupled cluster linear response calculations. Absorption oscillator strengths for dipole-allowed electronic transitions are also determined with the molecular-adapted quantum defect orbital methodology. Predictions of new spectroscopic data on SiH₄ are reported.

Article Outline

INTRODUCTION
COMPUTATIONAL DETAILS
RESULTS AND DISCUSSION
CONCLUSION

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KEYWORDS and PACS

Keywords

ab initio calculations, coupled cluster calculations, electron spectra, ionisation potential, Jahn-Teller effect, molecular configurations, molecule-electron collisions, orbital calculations, oscillator strengths, Rydberg states, silicon compounds

PACS

34.80.-i

Electron and positron scattering
33.70.Ca

Oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors
33.15.Ry

Ionization potentials, electron affinities, molecular core binding energy
33.15.Bh

General molecular conformation and symmetry; stereochemistry
31.15.ag

Excitation energies and lifetimes; oscillator strengths

ARTICLE DATA

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http://dx.doi.org/10.1063/1.3664629

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ISSN

0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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