Anharmonic vibrational spectroscopy of the F-(H2O)n complexes, n = 1, 2

Galina M. Chaban*, Sotiris S. Xantheas, R. Benny Gerber

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

63 Scopus citations

Abstract

We report anharmonic vibrational spectra (fundamentals, first overtones) for the F-(H2O) and F-(H2O)2 clusters computed at the MP2 and CCSD(T) levels of theory with basis sets of triple-ζ quality. Anharmonic corrections were estimated via the correlation-corrected vibration self-consistent field (CC-VSCF) method. The CC-VSCF anharmonic spectra obtained on the potential energy surfaces evaluated at the CCSD(T) level of theory are the first ones reported at a correlated level beyond MP2. We have found that the average basis set effect (TZP vs aug-cc-pVTZ) is on the order of 30-40 cm-1, whereas the effects of different levels of electron correlation [MP2 vs CCSD(T)] are smaller, 20-30 cm-1. However, the basis set effect is much larger in the case of the H-bonded O-H stretch of the F-(H2O) cluster amounting to 100 cm-1 for the fundamentals and 200 cm-1 for the first overtones. Our calculations are in agreement with the limited available set of experimental data for the F-(H2O) and F-(H2O)2 systems and provide additional information that can guide further experimental studies.

Original languageEnglish
Pages (from-to)4952-4956
Number of pages5
JournalJournal of Physical Chemistry A
Volume107
Issue number24
DOIs
StatePublished - 19 Jun 2003

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