An ab initio study of vibrational corrections to the electrical properties of the fluoromethanes: CH3F, CH2F2, CHF3 and CF4

AJ Russell, MA Spackman

Research output: Contribution to journalArticlepeer-review

Abstract

Accurate SCF and MP2 quartic property hypersurfaces have been computed for the energy, dipole moments, quadrupole moments and polarizability tensors of the fluorinated methanes CF4, CHF3, CH2F2 and CH3F, to establish accurate values of zero-point vibrational corrections to the properties. Using a consistent set of r(e) geometries from density functional theory, these ZPVCs are coupled with accurate electrical properties computed using a range of correlated methods, especially BD and BD(T), and a number of purpose-built polarized basis sets, to obtain near definitive estimates of these properties that incorporate the effects of vibrational averaging. Careful attention has been paid to a critical comparison between these theoretical estimates and experimental measurements, and agreement between the two is shown to be exceptionally good. In particular, it is clear that in many instances more precise experimental results would be required in order to discriminate between different correlated results, or between the present results and those which may be obtained with larger basis sets. The work highlights the necessity to allow for the effects of zero-point vibrational averaging when comparing theory with experiment, or even when comparing different theoretical results with one another using experiment as a benchmark. It also points to the need for further precise experimental measurements of some of these properties.

Original languageEnglish
Pages (from-to)633-642
Number of pages10
JournalMolecular Physics
Volume98
Issue number10
DOIs
Publication statusPublished - 20 May 2000
Externally publishedYes

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