Vibrational relaxation of trapped molecules in solid matrices: OH(A (2)Sigma(+);v=1)/Ar

Title
Vibrational relaxation of trapped molecules in solid matrices: OH(A (2)Sigma(+);v=1)/Ar
Authors
Ree, J.; Kim, Y.H.; Shin, H.K.
Keywords
RARE-GAS SOLIDS, ARGON MATRIX
Issue Date
2009-01
Publisher
AMER INST PHYSICS
Abstract
The vibrational relaxation of OH(A (2)Sigma(+);v=1) embedded in solid Ar has been studied over 4-80 K. The interaction model is based on OH undergoing local motions in a cage formed by a face-centered cubic stacking where the first shell atoms surround the guest and connect it to the heat bath through 12 ten-atom chains. The motions confined to the cage are the local translation and libration-rotation of OH and internal vibrations in OH center dot Ar, their energies being close to or a few times the energies of nearby first shell and chain atoms. The cage dynamics are studied by solving the equations of motion for the interaction between OH and first shell atoms, while energy propagation to the bulk phase through lattice chains is treated in the Langevin dynamics. Calculated energy transfer data are used in semiclassical procedure to obtain rate constants. In the early stage of interaction, OH transfers its energy to libration-rotation intramolecularily and then to the vibrations of the first shell and chain atoms on the time scale of several picoseconds. Libration-to-rotational transitions dispense the vibrational energy in small packages comparable to the lattice frequencies for ready flow. Energy propagation from the chains to the heat bath takes place on a long time scale of 10 ns or longer. Over the solid argon temperature range, the rate constant is on the order of 10(6) s(-1) and varies weakly with temperature.
URI
http://dspace.inha.ac.kr/handle/10505/1802
ISSN
0021-9606
Appears in Collections:
College of Natural Science(자연과학대학) > Chemistry (화학) > Journal Papers, Reports(화학 논문, 보고서)
Files in This Item:
Vibrational.pdfDownload

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Browse