TY - JOUR

T1 - Influence of resonance interactions and matrix environment on the spectra of SF6 dimers in low-temperature nitrogen matrixes. theory and experiment

AU - Tokhadze, Irina K.

AU - Kolomiitsova, Tatjana D.

AU - Shchepkin, Dmitrii N.

AU - Tokhadze, Konstantin G.

AU - Mielke, Zofia

N1 - Copyright: Copyright 2009 Elsevier B.V., All rights reserved.

PY - 2009/6/4

Y1 - 2009/6/4

N2 - The IR absorption spectra of (SF6)2 dimers were studied in N2 matrixes at 11 K. Absorption bands due to SF 6 monomers and to (SF6)2 dimers have been identified. As a result of the resonance dipole-dipole interaction between two SF6 subunits, the band of the triply degenerate vibration v 3 is split into two components vx,y and vz, where Z is the axis connecting the two sulfur atoms. The main distinction between the spectra of (SF6)2 dimers recorded here compared to spectra in the gas phase is the splitting of the vx,y component. A model that takes into account the influence of the matrix on the spectra of dimers is developed. The model makes it possible to successively (i) calculate the resonance spectrum of an isolated dimer in terms of the model of local modes including the resonance interactions, (ii) determine with the help of the Monte Carlo method the structure of a matrix consisting of 864 N 2 molecules and a rigid (SF6)2 dimer, and (iii) take into account the interactions of local dipole moments of a dimer with host particles in the approximation of dipole-induced dipole and dipole-quadrupole interactions. The calculated spectra sufficiently well reproduce the main characteristics of the experimental spectra in N2 matrixes, in particular, the decrease of the resonance splitting upon transition from the gas phase to a matrix and the splitting of vx,y component in the nitrogen matrix.

AB - The IR absorption spectra of (SF6)2 dimers were studied in N2 matrixes at 11 K. Absorption bands due to SF 6 monomers and to (SF6)2 dimers have been identified. As a result of the resonance dipole-dipole interaction between two SF6 subunits, the band of the triply degenerate vibration v 3 is split into two components vx,y and vz, where Z is the axis connecting the two sulfur atoms. The main distinction between the spectra of (SF6)2 dimers recorded here compared to spectra in the gas phase is the splitting of the vx,y component. A model that takes into account the influence of the matrix on the spectra of dimers is developed. The model makes it possible to successively (i) calculate the resonance spectrum of an isolated dimer in terms of the model of local modes including the resonance interactions, (ii) determine with the help of the Monte Carlo method the structure of a matrix consisting of 864 N 2 molecules and a rigid (SF6)2 dimer, and (iii) take into account the interactions of local dipole moments of a dimer with host particles in the approximation of dipole-induced dipole and dipole-quadrupole interactions. The calculated spectra sufficiently well reproduce the main characteristics of the experimental spectra in N2 matrixes, in particular, the decrease of the resonance splitting upon transition from the gas phase to a matrix and the splitting of vx,y component in the nitrogen matrix.

UR - http://www.scopus.com/inward/record.url?scp=66249094565&partnerID=8YFLogxK

U2 - 10.1021/jp902055m

DO - 10.1021/jp902055m

M3 - Article

AN - SCOPUS:66249094565

VL - 113

SP - 6334

EP - 6341

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 22

ER -