Accurate ab initio structure, dissociation energy, and vibrational spectroscopy of the F--CH4 anion complex

Gábor Czakó, Bastiaan J. Braams, Joel M. Bowman

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Abstract

Accurate equilibrium structure, dissociation energy, global potential energy surface (PES), dipole moment surface (DMS), and the infrared vibrational spectrum in the 0-3000 cm-1 range of the F--CH4 anion complex have been obtained. The equilibrium electronic structure calculations employed second-order Møller-Plesset perturbation theory (MP2) and coupled-cluster (CC) method up to single, double, triple, and perturbative quadruple excitations using the aug-cc-p(C)VXZ [X = 2(D), 3(T), 4(Q), and 5] correlation-consistent basis sets. The best equilibrium geometry has been obtained at the all-electron CCSD(T)/aug-cc-pCVQZ level of theory. The dissociation energy has been determined based on basis set extrapolation techniques within the focal-point analysis (FPA) approach considering (a) electron correlation beyond the all-electron CCSD(T) level, (b) relativistic effects, (c) diagonal Born-Oppenheimer corrections (DBOC), and (d) variationally computed zero-point vibrational energies. The final De and D 0 values are 2398 ±12 and 2280 ±20 cm-1, respectively. The global PES and DMS have been computed at the frozen-core CCSD(T)/aug-cc-pVTZ and MP2/aug-cc-pVTZ levels of theory, respectively. Variational vibrational calculations have been performed for CH4 and F--CH4 employing the vibrational configuration interaction (VCI) method as implemented in Multimode.

Original languageEnglish
Pages (from-to)7466-7472
Number of pages7
JournalJournal of Physical Chemistry A
Volume112
Issue number32
DOIs
Publication statusPublished - Aug 14 2008

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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