This paper describes the development
and testing of a polynomial
variety-based matrix completion (PVMC) algorithm. Our goal is to reduce
computational effort associated with reaction rate coefficient calculations
using variational transition state theory with multidimensional tunneling
(VTST-MT). The algorithm recovers eigenvalues of quantum mechanical
Hessians constituting the minimum energy path (MEP) of a reaction
using only a small sample of the information, by leveraging underlying
properties of these eigenvalues. In addition to the low-rank property
that constitutes the basis for most matrix completion (MC) algorithms,
this work introduces a polynomial constraint in the objective function.
This enables us to sample matrix columns unlike most conventional
MC methods that can only sample elements, which makes PVMC readily
compatible with quantum chemistry calculations as sampling a single
column requires one Hessian calculation. For various types of reactionsS
N
2, hydrogen atom transfer, metal–ligand
cooperative catalysis, and enzyme chemistrywe demonstrate
that PVMC on average requires only six to seven Hessian calculations
to accurately predict both quantum and variational effects.