Efficient Estimators for Quantum Instanton Evaluation of theKinetic Isotope Effects: Application to the Intramolecular HydrogenTransfer in Pentadiene

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The quantum instanton approximation is used to compute kinetic isotope effects for intramolecular hydrogen transfer in cis-1,3-pentadiene. Due to the importance of skeleton motions, this system with 13 atoms is a simple prototype for hydrogen transfer in enzymatic reactions. The calculation is carried out using thermodynamic integration with respect to the mass of the isotopes and a path integral Monte Carlo evaluation of relevant thermodynamic quantities. Efficient 'virial' estimators are derived for the logarithmic derivatives of the partition function and the delta-delta correlation functions. These estimators require significantly fewer Monte Carlo samples since their statistical error does not increase with ... continued below

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Vanicek, Jiri & Miller, William H. June 13, 2007.

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The quantum instanton approximation is used to compute kinetic isotope effects for intramolecular hydrogen transfer in cis-1,3-pentadiene. Due to the importance of skeleton motions, this system with 13 atoms is a simple prototype for hydrogen transfer in enzymatic reactions. The calculation is carried out using thermodynamic integration with respect to the mass of the isotopes and a path integral Monte Carlo evaluation of relevant thermodynamic quantities. Efficient 'virial' estimators are derived for the logarithmic derivatives of the partition function and the delta-delta correlation functions. These estimators require significantly fewer Monte Carlo samples since their statistical error does not increase with the number of discrete time slices in the path integral. The calculation treats all 39 degrees of freedom quantum-mechanically and uses an empirical valence bond potential based on a modified general AMBER force field.

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  • Journal Name: Journal of Chemical Physics; Journal Volume: 127; Related Information: Journal Publication Date: 2007

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  • Report No.: LBNL--63540
  • Grant Number: DE-AC02-05CH11231
  • DOI: 10.1063/1.2768930 | External Link
  • Office of Scientific & Technical Information Report Number: 919273
  • Grant Number: N00014-05-1-0457
  • Archival Resource Key: ark:/67531/metadc887568

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  • June 13, 2007

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  • Sept. 22, 2016, 2:13 a.m.

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  • Nov. 27, 2017, 6:26 p.m.

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Vanicek, Jiri & Miller, William H. Efficient Estimators for Quantum Instanton Evaluation of theKinetic Isotope Effects: Application to the Intramolecular HydrogenTransfer in Pentadiene, article, June 13, 2007; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc887568/: accessed December 12, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.