Nuclear quantum effects in chemical reactions via higher-order path-integral calculations

摘要: Abstract A practical approach to treat nuclear quantum mechanical effects in simulations of condensed phases, such as enzymes, is via Feynman path integral (PI) formulations. Typically, the standard primitive approximation (PA) employed enzymatic PI simulations. Nonetheless, these are computationally demanding due large number beads required obtain converged results. The efficiency may be greatly improved if higher-order factorizations density matrix operator employed. Herein, we compare results model calculations obtained employing PA, Takahashi and Imada (TI), a gradient-based forward corrector algorithm Chin (CH). transmission coefficient computed for Eckart potential while partition functions rate constant H 2  + H hydrogen transfer reaction. These potentials simple models chemical reactions. study different factorization methods reveals that most cases action converges faster than PA TI approaches, at moderate computational cost.