The molecular structure of selenium dibromide as determined by combined gas-phase electron diffraction–mass spectrometric experiments and quantum chemical calculations
- 22 September 2008
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Physical Chemistry Chemical Physics
- Vol. 10 (42) , 6438-6445
Abstract
The vapour over solid SeBr4 at 10 °C was investigated with a combined gas-phase electron diffraction/mass spectrometric (GED/MS) method. The composition of the vapour derived from the mass spectra (43% SeBr2, 56.7% Br2 and 0.3% Se2Br2) was in agreement with the composition obtained from the analysis of the simultaneously recorded GED intensities (41(3)% SeBr2, 59(3)% Br2). The GED study results in the following geometric parameters (rg, ∠g values with total uncertainties): Se–Br = 2.306(5) Å and Br–Se–Br = 101.6(6)°. Most quantum chemical approximations (B3LYP, MP2, CCSD and CCSD(T) with relativistic effective core potentials and cc-pVTZ as well as aug-cc-pVTZ basis sets for the outer shells) overestimate the Se–Br bond length by 0.01 to 0.03 Å. All methods reproduce the bond angle correctly, except for the B3LYP method. Gas phase vibrational frequencies estimated from experimental vibrational amplitudes agree well with those measured by Raman spectroscopy in acetonitrile solutions. All computational methods overestimate vibrational frequencies, especially that for the symmetric stretch vibration, by about or 8 to 13%.Keywords
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