Pj. Stephens et al., AB-INITIO CALCULATION OF ATOMIC AXIAL TENSORS AND VIBRATIONAL-ROTATIONAL STRENGTHS USING DENSITY-FUNCTIONAL THEORY, Molecular physics, 89(2), 1996, pp. 579-594
We document a new density functional theory (DFT) methodology for the
ab initio calculation of atomic axial tensors (AATs) using direct, ana
lytical derivative methods and gauge-invariant atomic orbital (GIAO) b
asis sets. AATs are calculated for ethylene oxide. Their accuracy is a
ssessed using AAT sum rules and the experimental electric dipole momen
t and paramagnetic susceptibility tensor. AATs calculated for the chir
al molecule 6,8-dioxabicyclo[3.2.1]octane, in combination with DFT har
monic force fields and atomic polar tensors, are used to predict vibra
tional rotational strengths and vibrational circular dichroism (VCD) s
pectra. Their accuracy is assessed by comparison with the experimental
rotational strengths and VCD spectrum. The dependence of calculated r
esults on density functional and basis set is explored. The DFT calcul
ations are compared to SCF (Hartree-Fock) calculations carried out in
parallel.