Mode-specific intermolecular vibrational energy transfer. I. Phenyl selenocyanate and deuterated chloroform mixture

Vibrational energy transfer from the first excited state 2252 cm−1 of the C–D stretch of deuterated chloroform DCCl3 to the 0-1 transition 2155 cm−1 of the CN stretch of phenyl selenocyanate C6H5SeCN in their 1:1 liquid mixture was observed with a pump/probe two-color two dimensional infrared spectroscopic technique. The mode-specific energy transfer can occur mainly because of the long vibrational lifetime of the CN stretch first excited state 300 ps and the relatively strong hydrogen-bond between the C–D and CN calculated H-bond formation energy in gas phase −5.4 kcal /mol . The mode-specific energy transfer is relatively low efficient only 2% , which is mainly because of the relatively short vibrational lifetime 9 ps of the C–D stretch first excited state and the big donor/acceptor energy mismatch 97 cm−1 and the slow transfer kinetics 1 /kCD→CN=330 ps . © 2010 American Institute of Physics. doi:10.1063/1.3429170