TY - EJOUR
DO - 10.1007/s00894-010-0711-y
AB - Recent experiments have confirmed the importance of nuclear quantum effects even in large biomolecules at physiological temperature. Here we describe how the path integral formalism can be used to describe rigorously the nuclear quantum effects on equilibrium and kinetic properties of molecules. Specifically, we explain how path integrals can be employed to evaluate the equilibrium (EIE) and kinetic (KIE) isotope effects, and the temperature dependence of the rate constant. The methodology is applied to the [1,5] sigmatropic hydrogen shift in pentadiene. Both the KIE and the temperature dependence of the rate constant confirm the importance of tunneling and other nuclear quantum effects as well as of the anharmonicity of the potential energy surface. Moreover, previous results on the KIE were improved by using a combination of a high level electronic structure calculation within the harmonic approximation with a path integral anharmonicity correction using a lower level method.
T1 - Three applications of path integrals: equilibrium and kinetic isotope effects, and the temperature dependence of the rate constant of the [1,5] sigmatropic hydrogen shift in (Z)-1,3-pentadiene
IS - 11
DA - 2010
AU - Zimmermann, Tomas
AU - Vanicek, Jiri
JF - Journal of Molecular Modeling
SP - 1779-1787
VL - 16
EP - 1779-1787
PB - Springer Verlag
ID - 148664
KW - Anharmonicity effects
KW - Equilibrium isotope effect
KW - Kinetic isotope effect
KW - Path integral
KW - Quantum instanton
KW - Rotational-vibrational coupling
KW - [1,5] Sigmatropic hydrogen shift
KW - Temperature dependence of the rate constant
KW - Tunneling
SN - 1610-2940
UR - http://www.springerlink.com/content/98m742j010526107/?p=b00669a7cf9f4763a44676c8a7f6b0e8&pi=2
UR - http://infoscience.epfl.ch/record/148664/files/JMolModel2010_1.pdf
ER -