Contribution of the asymmetric stretch, ν B , to the fundamental Raman spectrum of water
Journal of Chemical Physics, ISSN: 0021-9606, Vol: 124, Issue: 18, Page: 184505
2006
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Article Description
The OD-stretching overtone from liquid D O, 2ν, and the fundamental OD stretch from dilute HDO, both display high-frequency depolarization ratio minima, but the fundamental OD stretch from neat D displays a maximum, at the equivalent position. The ρ L minima arises from the decreased depolarization ratio produced by the absence of B1 modes. The fundamentals of HDO are of A species, and the 2ν overtone of D only involves A1 species, e.g., 2 ν3 B1 has A1 species via B1 × B1 = A1. A and A1 modes display small ρ L values which produce minima in ρ L near 2665 cm-1 for HDO, and near 5250 cm-1 for the D overtone. These minima give way to a depolarization ratio maximum when the depolarized, ρ L =34, ν3 B1 fundamental, makes its appearance in D at 2650 cm-1. Fundamental and overtone depolarization ratios were used to determine the ν3 B1 contribution to the depolarization ratio of the fundamental OD stretch; a value of ≈28% resulted at 2655 cm-1. Liquid H2 O displays completely analogous features; a value of ≈20% resulted for it at 3660 cm-1. Nonhydrogen-bonded ν3 B1, and more strongly hydrogen-bonded ν3 B1, modes are also indicated for D2 O and H . A rigorous test of the current results can be accomplished by measuring the depolarization ratio of the extraordinarily weak second Raman overtone, 3ν, recently detected for D . © 2006 American Institute of Physics.
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