TY - JOUR

T1 - Path-integral calculations of heavy atom kinetic isotope effects in condensed phase reactions using higher-order trotter factorizations

AU - Vardi-Kilshtain, Alexandra

AU - Azuri, Asaf

AU - Major, Dan Thomas

PY - 2012/2/5

Y1 - 2012/2/5

N2 - 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.

AB - 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.

KW - 1-methyl orotate

KW - kinetic isotope effect

KW - orotidine 5′-monophosphate decarboxylase

KW - path-integral

KW - quantum mechanics/molecular mechanics

UR - http://www.scopus.com/inward/record.url?scp=84855650215&partnerID=8YFLogxK

U2 - 10.1002/jcc.21986

DO - 10.1002/jcc.21986

M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???

C2 - 22121039

SN - 0192-8651

VL - 33

SP - 435

EP - 441

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

IS - 4

ER -