The benzene ground state potential surface. IV. Discrimination between multiple E1u force field solutions through infrared intensities

Abstract

Accurate values for integrated intensities of the infrared active 13C6H6 fundamentals, ν18, ν19, ν20, and ν11 (Wilson notation) have been measured and redetermined for ν18 and ν19 in C6H6 and C6D6. The 13C6H6 intensities are I18=6.52±0.15, I19=12.60±0.20, I20=55.6±1, and I11=74.6±3 km/mol. Unlike C6H6 and C6D6, interfering transitions in 13C6H6 are minor and these intensities can be used as a critical test for theoretical predictions of atomic polar tensors. The ν18 intensities in C6H6 and C6D6 (7.48±0.15 and 7.09±0.14 km/mol, respectively) and the ν19 intensity in C6D6 (2.51±0.12 km/mol) are measured to be substantially lower than the literature values. The qualitative intensity pattern of benzene in-plane fundamentals uniquely discriminate among the eight possible real E1u force field solutions obtained from frequency information alone. Isotopically invariant dipole moment derivatives, ∂μ/∂S18a, ∂μ/∂S19a, and ∂μ/∂S20a are 0.494±0.005, 0.395±0.016, and 0.770±0.008 D/Å, respectively, obtained from the 13C6H6 experimental intensities and the complete experimental force field of Part II. Using these quantities and the L−1 matrix (Table III), dipole moment gradients for C6H6 become ∂μ/∂Q018a =+0.298, ∂μ/∂Q019a =+0.371, and ∂μ/∂Q020a =+0.814 D/Å. Mode decomposition matrices expressing normal modes of benzene in terms of isotopically labeled molecule modes have been used to definitively determine the C6H6 dipole gradient signs. The signs are in agreement with theoretical calculations. The D6 isotopic labeling effect on C6H6 ν18 intensity provides a sensitive test of E1u force field quality and reveals the inadequacy of present theoretical force field approaches. Ab initio atomic polar tensors have been obtained both at the HF level, using several basis sets up to the 6-311+G(d,p) and at the MP2 level up to the 6-31+G(d) basis set. The dipole derivative for the CC stretch is highly sensitive to both basis set (particularly diffuse functions) and correlation effects. Qualitative CH and CC stretching dipole derivative and intensity predictions by the MP2/6-31+G(d) calculation are encouraging (i.e., within 15% of the experimental values). However, the same calculation yields 20% and 45% errors for the CH bending dipole derivative and fundamental intensity, respectively.