Exploring the Origins of the Intensity of the OH Stretch-HOH Bend Combination Band in Water.

Abstract

While the intensity of the OH stretching fundamental transition is strongly correlated to hydrogen-bond strength, the intensity of the corresponding transition to the state with one quantum of excitation in both the OH stretching and HOH bending vibrations in the same water molecule shows a much weaker sensitivity to the hydrogen-bonding environment. The origins of this difference are explored through analyses of the contributions of terms in the expansion of the dipole moment to the calculated intensity. It is found that the leading contribution to the stretch-bend intensity involves the second derivative of the dipole moment with respect to the OH bond length and HOH angle. While this is not surprising, the insensitivity of this derivative to the hydrogen-bonding environment is unexpected. Possible contributions of mode mixing are also explored. While mode mixing leads to splittings of the energies of nearly degenerate excited states, it does not result in significant changes in the sum of the intensities of these transitions. Analysis of changes in the partial charges on the hydrogen atoms upon displacement of the HOH angles shows that these charges generally increase with increasing HOH angle. This effect is partially canceled by a decrease in the charge of the hydrogen atom when a hydrogen bond is broken. The extent of this cancellation increases with the hydrogen bond strength, which is reflected in the observed insensitivity of the intensity of the stretch-bend transition to hydrogen-bond strength.