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arXiv:2206.08973 · Journal of Chemical Theory and Computation

Optimization Stability in Excited-State-Specific Variational Monte Carlo

Leon Otis, Eric Neuscamman

Published Jan 20, 2023• 10 citations
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Abstract

We investigate the issue of optimization stability in variance-based state-specific variational Monte Carlo, discussing the roles of the objective function, the complexity of wave function ansatz, the amount of sampling effort, and the choice of minimization algorithm. Using a small cyanine dye molecule as a test case, we systematically perform minimizations using variants of the linear method as both a standalone algorithm and in a hybrid combination with accelerated descent. We demonstrate that adaptive step control is crucial for maintaining the linear method's stability when optimizing complicated wave functions and that the hybrid method enjoys both greater stability and minimization performance.

DOI
10.1021/acs.jctc.2c00642

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