Dipole moment derivatives with respect to the internal coordinates of benzene in the liquid and gas phases

This paper presents a comparison of the dipole moment derivatives with respect to internal coordinates in the liquid and gas phases for benzene-h(6), benzene-d(6) and benzene-d(1). The literature values of the integrated intensities of the infrared active fundamentals of the three gaseous isotopomers are used to determine the dipole moment derivatives with respect to internal coordinates, using the methods described in the previous paper for the liquid phase. As was found for the liquid phase in the previous paper, there is uncertainty surrounding the intensities of the individual CH stretching fundamentals of benzene-d(1) due to intensity sharing with active combinations. The magnitudes of the dipole moment derivatives with respect to internal coordinates in the gas phase are partial derivative mu/partial derivative s=0.50 +/- 0.03 D angstrom(-1), partial derivative mu/partial derivative beta=0.28 +/- 0.03, partial derivative mu/partial derivative beta=0.24 +/- 0.01, and partial derivative mu/partial derivative gamma=0.65 +/- 0.02 D angstrom(-1), where s, t, beta and gamma are the CH stretching, and CC stretching, the HCC bending and the HCCC torsion displacements, respectively. The experimental intensities are different for the three isotoporners in the liquid and gas phases, and the calculations show that these differences are mainly due to a difference between the CH stretch dipole moment derivatives in the two phases. This difference was related qualitatively to the intermolecular interaction of the H with the pi cloud of the nearest neighbour creating a pseudo-hydrogen bond. (c) 2005 Elsevier B.V. All rights reserved.