Perturbatively corrected ring-polymer instanton theory for accurate tunneling splittings.

We introduce an approach for calculating perturbative corrections to the ring-polymer instanton approximation to tunneling splittings (RPI+PC) by computing higher-order terms in the asymptotic expansion in ℏ. The resulting method goes beyond standard instanton theory by using information on the third and fourth derivatives of the potential along the tunneling path to include additional anharmonic effects. This leads to significant improvements both in systems with low barriers and in systems with anharmonic modes. We demonstrate the applicability of RPI+PC to molecular systems by computing the tunneling splitting in full-dimensional malonaldehyde and a deuterated derivative. Comparing to both experiment and recent quantum mechanical benchmark results, we find that our perturbative correction reduces the error from -11% to 2% for hydrogen transfer and performs even better for the deuterated case. This makes our approach more accurate than previous calculations using diffusion Monte Carlo and path-integral molecular dynamics while being more computationally efficient.