Efficient and Stochastic Multireference Perturbation Theory for Large Active Spaces within a Full Configuration Interaction Quantum Monte Carlo Framework

TL;DR

This paper introduces a stochastic method within FCIQMC for efficiently computing NEVPT2 in large active spaces, enabling accurate multireference calculations that surpass traditional methods in practicality.

Contribution

It develops a stochastic approach for NEVPT2 within FCIQMC, demonstrating stability and efficiency for large active spaces and complex chemical systems.

Findings

NEVPT2 is more stable than CASPT2 in stochastic reformulation.

Small numbers of walkers suffice for chemical accuracy in large active spaces.

The method enables practical multireference calculations beyond traditional limits.

Abstract

Full Configuration Interaction Quantum Monte Carlo (FCIQMC) has been effectively applied to very large configuration interaction (CI) problems, and was recently adapted for use as an active space solver and combined with orbital optimisation. In this work, we detail an approach within FCIQMC to allow for efficient sampling of fully internally-contracted multireference perturbation theories within the same stochastic framework. Schemes are described to allow for the close control over the resolution of stochastic sampling of the effective higher-body intermediates within the active space. It is found that while CASPT2 seems less amenable to a stochastic reformulation, NEVPT2 is far more stable, requiring a similar number of walkers to converge the NEVPT2 expectation values as to converge the underlying CI problem. We demonstrate the application of the stochastic approach to the computation of NEVPT2 within a (24,24) active space in a biologically relevant system, and show that small numbers of walkers are sufficient for a faithful sampling of the NEVPT2 energy to chemical accuracy, despite the active space already exceeding the limits of practicality for traditional approaches. This raises prospects of an efficient stochastic solver for multireference chemical problems requiring large active spaces, with an accurate treatment of external orbitals.