Nonadiabatic excited-state dynamics with quantum Monte Carlo-trained machine learning: azomethane as a stringent test
TL;DR
QMC-ML is established as a practical route to nonadiabatic photochemical dynamics with accurate wave-function reference data, targeting photochemical processes in which the electronic character changes along the reaction path and a consistent correlated description is required.
Abstract
We introduce quantum Monte Carlo (QMC)-trained multi-state machine-learned (ML) force fields for nonadiabatic excited-state dynamics, targeting photochemical processes in which the electronic character changes along the reaction path and a consistent correlated description is required. In this framework, variational Monte Carlo wave functions combine compact selected configuration-interaction expansions with a Jastrow factor that explicitly accounts for dynamical correlation, while neural networks convert the stochastic QMC data into smooth potential energy surfaces for large surface-hopping ensembles. We apply this approach to azomethane, a demanding test case involving torsional relaxation through conical-intersection regions and C--N bond dissociation on the hot ground state. Benchmark calculations support the accuracy of the QMC reference data and show robust force convergence across isomerization and dissociation geometries. The QMC-trained dynamics preserves the expected photoisomerization mechanism, strongly reduces the excessive C--N breaking obtained with complete active space self-consistent field, and predicts a small but non-negligible prompt dissociation component after internal conversion, with a timescale consistent with femtosecond-resolved mass-spectrometry experiments. These results establish QMC-ML as a practical route to nonadiabatic photochemical dynamics with accurate wave-function reference data.