000148664 001__ 148664
000148664 005__ 20180913055750.0
000148664 0247_ $$2doi$$a10.1007/s00894-010-0711-y
000148664 022__ $$a1610-2940
000148664 02470 $$2ISI$$a000282515400012
000148664 037__ $$aARTICLE
000148664 245__ $$aThree applications of path integrals: equilibrium and kinetic isotope effects, and the temperature dependence of the rate constant of the [1,5] sigmatropic hydrogen shift in (Z)-1,3-pentadiene
000148664 269__ $$a2010
000148664 260__ $$bSpringer Verlag$$c2010
000148664 336__ $$aJournal Articles
000148664 520__ $$aRecent 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. 
000148664 6531_ $$aAnharmonicity effects
000148664 6531_ $$aEquilibrium isotope effect
000148664 6531_ $$aKinetic isotope effect
000148664 6531_ $$aPath integral
000148664 6531_ $$aQuantum instanton
000148664 6531_ $$aRotational-vibrational coupling
000148664 6531_ $$a[1,5] Sigmatropic hydrogen shift
000148664 6531_ $$aTemperature dependence of the rate constant
000148664 6531_ $$aTunneling 
000148664 700__ $$0242994$$aZimmermann, Tomas$$g187721
000148664 700__ $$0240352$$aVanicek, Jiri$$g181577
000148664 773__ $$j16$$k11$$q1779-1787$$tJournal of Molecular Modeling
000148664 8564_ $$uhttp://www.springerlink.com/content/98m742j010526107/?p=b00669a7cf9f4763a44676c8a7f6b0e8&pi=2$$zURL
000148664 8564_ $$s225860$$uhttps://infoscience.epfl.ch/record/148664/files/JMolModel2010_1.pdf$$zn/a
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000148664 937__ $$aEPFL-ARTICLE-148664
000148664 973__ $$aEPFL$$rREVIEWED$$sPUBLISHED
000148664 980__ $$aARTICLE