Journal article
Structure and Heats of Formation of Iodine Fluorides and the Respective Closed-Shell Ions from CCSD(T) Electronic Structure Calculations and Reliable Prediction of the Steric Activity of the Free-Valence Electron Pair in CIF sub(6) super(-), BrF sub(6) super(-), and IF sub(6) super(-)
Inorganic chemistry, Vol.47(12), pp.5485-5494
06/16/2008
Handle:
https://hdl.handle.net/2376/112824
Abstract
Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for IF, IF sub(2) super(-), IF sub(2) super(+), IF sub(3), IF sub(4) super(-), IF sub(4) super(+), IF sub(5), IF sub(6) super(-), IF sub(6) super(+), IF sub(7), IF sub(8) super(-), BrF sub(6) super(-), and CIF sub(6) super(-) from coupled cluster theory [CCSD(T)] calculations with effective-core potential correlation-consistent basis sets for I. In order to achieve near chemical accuracy (+ or -1 kcal/mol), three corrections were added to the complete basis set binding energies based on frozen-core coupled-cluster theory energies: a correction for core-valence effects, a correction for scalar relativistic effects, and a correction for first-order atomic spin-orbit effects. Vibrational zero-point energies were computed at the coupled-cluster level of theory except for IF sub(6) super(-), IF sub(7), and IF sub(3) super(-). The calculated heats of formation for the neutral and ionic IF sub()nfluorides were used to predict fluoride affinities. It is shown that high-level calculations are required to predict correctly the steric activity of the free-valence electron pair on the central atoms in IF sub(6) super(-) (C sub(3)v, BrFg super(-) (O sub()h, and CIF sub(6) super(-) (O sub()h. The vibrational spectrum of IF sub(8) super(-) was reanalyzed, and complete mode descriptions for square-antiprismatic XF sub(3) species of D sub(4)dsymmetry are given.
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- Title
- Structure and Heats of Formation of Iodine Fluorides and the Respective Closed-Shell Ions from CCSD(T) Electronic Structure Calculations and Reliable Prediction of the Steric Activity of the Free-Valence Electron Pair in CIF sub(6) super(-), BrF sub(6) super(-), and IF sub(6) super(-)
- Creators
- David A DixonDaniel J GrantKarl O ChristeKirk A Peterson
- Publication Details
- Inorganic chemistry, Vol.47(12), pp.5485-5494
- Academic Unit
- Chemistry, Department of
- Identifiers
- 99900547890901842
- Language
- English
- Resource Type
- Journal article