Mode-specific intermolecular vibrational energy transfer. II. Deuterated water and potassium selenocyanate mixture

Hongtao Bian; Xiewen Wen; Jiebo Li; Junrong Zheng

doi:10.1063/1.3458825

Mode-specific intermolecular vibrational energy transfer. II. Deuterated water and potassium selenocyanate mixture

J Chem Phys. 2010 Jul 21;133(3):034505. doi: 10.1063/1.3458825.

Authors

Hongtao Bian¹, Xiewen Wen, Jiebo Li, Junrong Zheng

Affiliation

¹ Department of Chemistry, Rice University, Houston, Texas 77005, USA.

PMID: 20649335
DOI: 10.1063/1.3458825

Abstract

Vibrational energy transfer from the first excited state (2635 cm(-1)) of the O-D stretch of deuterated water (D(2)O) to the 0-1 transition (2075 cm(-1)) of the CN stretch of potassium selenocyanate (KSeCN) in their 2.5:1 liquid mixture was observed with a multiple-mode two dimensional infrared spectroscopic technique. Despite the big energy mismatch (560 cm(-1)) between the two modes, the transfer is still very efficient with a time constant of 20 ps. The efficient energy transfer is probably because of the large excitation coupling between the two modes. The coupling is experimentally determined to be 176 cm(-1). An approximate analytical equation derived from the Landau-Teller formula is applied to calculate the energy transfer rate with all parameters experimentally determined. The calculation results are qualitatively consistent with the experimental data.