Quantum mechanical modeling for the GeX2/GeHX + GeH4 reactions (X = H, F, Cl, and Br)

Ashwini Bundhun, Paul Blowers, Ponnadurai Ramasami, Henry F. Schaefer

Research output: Contribution to journalArticle

3 Scopus citations

Abstract

A systematic theoretical investigation was carried out to study the reactions of various germylenes with germane. Molecular structures of the reactants (GeX2 and GeHX, where X = H, F, Cl and Br) plus GeH 4, transition states, and products have been optimized to understand the effects of halo-substituted germylenes. The basis set used is of double-ζ plus polarization quality with additional s- and p-type diffuse functions. Consistent with experiment, the theoretical gas-phase reaction GeH2 + GeH4 → Ge2H6 possesses a negative activation energy. The predicted activation energies reveal interesting trends for both mono- and di- halo-substituted germylenes, - 1.5 [GeH2], + 20.5 [GeHF], +59.9 [GeF2], +18.0 [GeHCl], +46.8 [GeCl2], +17.3 [GeHBr], and +42.9 kcal mol-1 [GeBr 2]. There is a noteworthy relationship between the activation energies and the singlet-triplet splittings of the divalent germylenes. We report for the first time rate constants for the transfer of hydrogen, evaluated using standard transition-state theory with tunneling corrections. These results are analyzed and compared to the available experimental and previous theoretical findings for the gas-phase reactions involving germylene derivatives and germanium analogues.

Original languageEnglish (US)
Pages (from-to)4210-4223
Number of pages14
JournalJournal of Physical Chemistry A
Volume114
Issue number12
DOIs
StatePublished - Apr 1 2010

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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