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Keywords:

  • quantum mechanics/molecular mechanics;
  • path-integral;
  • kinetic isotope effect;
  • 1-methyl orotate;
  • orotidine 5′-monophosphate decarboxylase

Abstract

A convenient approach to compute kinetic isotope effects (KIEs) in condensed phase chemical reactions is via path integrals (PIs). Usually, the primitive approximation is used in PI simulations, although such quantum simulations are computationally demanding. The efficiency of PI simulations may be greatly improved, if higher-order Trotter factorizations of the density matrix operator are used. In this study, we use a higher-order PI method, in conjunction with mass-perturbation, to compute heavy-atom KIE in the decarboxylation of orotic acid in explicit sulfolane solvent. The results are in good agreement with experiment and show that the mass-perturbation higher-order Trotter factorization provides a practical approach for computing condensed phase heavy-atom KIE. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2012