Journal article
The Use of Explicitly Correlated Methods on XeF6 Predicts a C 3v Minimum with a Sterically Active, Free Valence Electron Pair on Xe
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.116(39), pp.9777-9782
10/04/2012
Handle:
https://hdl.handle.net/2376/107670
PMID: 22963178
Abstract
Explicitly correlated CCSD(T)-F12b calculations show that the lowest energy conformer of XeF6 is the C 3v structure with a stereoactive lone pair. The C 3v structure is 1.08 kcal/mol below the C 2v structure and 1.80 kcal/mol below the Oh structure without vibrational corrections. The C 2v conformer is a transition state connecting the different C 3v minima on the pseudorotation potential energy surface, and the Oh structure is a higher-order saddle point leading to the C 2v transition states. The calculated vibrational frequencies for the C 3v structure best fit the experimental frequencies. The calculated heats of formation for XeF6, −62.1 ± 1.4 kcal/mol at 0 K and −64.0 ± 1.4 kcal/mol at 298 K, are the best available values and show that there are serious issues with the experimental values. The results show that the explicitly correlated CCSD(T)-F12b method can be used to address important electronic structure issues with smaller basis sets.
Metrics
7 Record Views
Details
- Title
- The Use of Explicitly Correlated Methods on XeF6 Predicts a C 3v Minimum with a Sterically Active, Free Valence Electron Pair on Xe
- Creators
- Kirk A PetersonDavid A DixonHermann Stoll
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.116(39), pp.9777-9782
- Academic Unit
- Chemistry, Department of
- Publisher
- American Chemical Society
- Identifiers
- 99900547431001842
- Language
- English
- Resource Type
- Journal article