We present the first single-reference calculations of
the atomic
axial tensors (AATs) with wave function-based methods including dynamic
electron correlation effects using second-order Møller–Plesset
perturbation theory (MP2) and configuration interaction doubles (CID).
Our implementation involves computing the overlap of numerical derivatives
of the correlated wave functions with respect to both nuclear displacement
coordinates and the external magnetic field. Out test set included
three small molecules, including the axially chiral hydrogen molecule
dimer and (P)-hydrogen peroxide, and the achiral
H2O. For our molecular test set, we observed deviations
of the AATs for MP2 and CID from that of the Hartree–Fock (HF)
method upward of 49%, varying with the choice of basis set. For (P)-hydrogen peroxide, electron correlation effects on the
vibrational circular dichroism (VCD) rotatory strengths and corresponding
spectra were particularly significant, with maximum deviations of
the rotatory strengths of 62 and 49% for MP2 and CID, respectively,
using our largest basis set. The inclusion of dynamic electron correlation
to the computation of the AATs can have a significant impact on the
resulting rotatory strengths and VCD spectra.