Transcorrelated methods for multireference problems.

Abstract

We apply the transcorrelated method to problems of multireference character. For this, we show that the choice of reference wavefunction during the Jastrow optimization procedure is vital, and we propose a workflow wherein we use conventional multi-configurational methods to provide a reference wavefunction for Jastrow factor optimization. This Jastrow function is subsequently used with transcorrelated-full configuration interaction quantum Monte Carlo within the xTC approximation to yield highly accurate transcorrelated energies. This is demonstrated for N2 using the aug-cc-pVTZ basis set, achieving chemical accuracy across the entire binding curve compared with experiment. We also apply the method to compute excitation energies of dinitrogen, CO, and the ammonia molecule, where accurate results, comparable to the best available theoretical predictions, are obtained with modest basis sets.