Basis set convergence of atomic axial tensors obtained from self-consistent field calculations using London atomic orbitals

Abstract

Hartree–Fock calculations of atomic axial tensors (AATs) and atomic polar tensors (APTs) are presented for HF, H2O, NH3, CH4, cyclopropane, carbodiimide, allene, and oxirane. London atomic orbitals are used for the axial tensors. The basis set convergence of the London AATs is found to be considerably faster than for the distributed origins (DO) approach. Indeed, the convergence of the London axial tensors is comparable to that of the polar tensors, indicating that the differential intensities of vibrational circular dichroism can be calculated as accurately as the total intensities of infrared spectroscopy. Dipole and rotational strengths are reported for NHDT, trans-cyclopropane-1,2-d2, carbodiimide, allene-1,3-d2, and trans-oxirane-2,3-d2.