Vibrational relaxation of C-D stretching vibrations in CDCl3, CDBr3, and CDI3 |
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Authors: | Gündo?du Kenan Nydegger Michael W Bandaria Jigar N Hill Sarah E Cheatum Christopher M |
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Institution: | Chemistry Department, The University of Iowa, Iowa City, IA 52242, USA. |
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Abstract: | We present time-resolved transient grating measurements of the vibrational relaxation rates of the C-D stretching vibrations of deuterated haloforms in benzene and acetone. We compare our results with previous measurements of excited C-H stretches in the same solvents to obtain insight into the solvent effect on the vibrational relaxation. In deuterated molecules, there are more low-order-coupled states and the states are closer in energy to the C-D stretch than in the unlabeled isotopologs. Therefore, the relaxation is faster for the deuterated molecules. The relaxation also shows a significant solvent dependence. Bromoform and iodoform form charge-transfer complexes with both benzene and acetone which enhance the relaxation rate. For chloroform, hydrogen bonding to acetone is expected to be a more favorable interaction. Surprisingly, however, the vibrational relaxation of CDCl(3) is slower in acetone than in benzene. |
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