A quantum generalization of intrinsic reaction coordinate using path integral centroid coordinates

The Journal of Chemical Physics
Motoyuki Shiga, Hiroshi Fujisaki

Abstract

We propose a generalization of the intrinsic reaction coordinate (IRC) for quantum many-body systems described in terms of the mass-weighted ring polymer centroids in the imaginary-time path integral theory. This novel kind of reaction coordinate, which may be called the "centroid IRC," corresponds to the minimum free energy path connecting reactant and product states with a least amount of reversible work applied to the center of masses of the quantum nuclei, i.e., the centroids. We provide a numerical procedure to obtain the centroid IRC based on first principles by combining ab initio path integral simulation with the string method. This approach is applied to NH(3) molecule and N(2)H(5) (-) ion as well as their deuterated isotopomers to study the importance of nuclear quantum effects in the intramolecular and intermolecular proton transfer reactions. We find that, in the intramolecular proton transfer (inversion) of NH(3), the free energy barrier for the centroid variables decreases with an amount of about 20% compared to the classical one at the room temperature. In the intermolecular proton transfer of N(2)H(5) (-), the centroid IRC is largely deviated from the "classical" IRC, and the free energy barrier is reduced by th...Continue Reading

References

Feb 9, 1987·Physical Review Letters·M J Gillan
Sep 25, 2002·Proceedings of the National Academy of Sciences of the United States of America·Alessandro Laio, Michele Parrinello
Mar 3, 2005·The Journal of Chemical Physics·Takeshi Yamamoto, William H Miller
Aug 25, 2005·Journal of the American Chemical Society·Masanori Tachikawa, Motoyuki Shiga
May 5, 2007·The Journal of Chemical Physics·Weinan EEric Vanden-Eijnden
Aug 30, 2007·Proceedings of the National Academy of Sciences of the United States of America·Thomas F MillerDavid Chandler
Jan 23, 2008·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Hiroaki IshibashiMasanori Tachikawa
May 12, 2009·The Journal of Chemical Physics·Rosana Collepardo-GuevaraDavid E Manolopoulos
Jul 2, 2009·The Journal of Chemical Physics·Anthony GoodrowMartin Head-Gordon
Nov 21, 2009·Proceedings of the National Academy of Sciences of the United States of America·Dan T MajorJiali Gao
Dec 9, 2009·The Journal of Chemical Physics·Jeremy O Richardson, Stuart C Althorpe
Dec 17, 2009·The Journal of Chemical Physics·Dimitri Antoniou, Steven D Schwartz
Mar 25, 2010·The Journal of Chemical Physics·Motoyuki ShigaMasanori Tachikawa
Feb 2, 2011·The Journal of Chemical Physics·Yury V SuleimanovDavid E Manolopoulos
Mar 3, 2011·The Journal of Chemical Physics·Victor OvchinnikovEric Vanden-Eijnden
Jul 27, 2011·The Journal of Chemical Physics·S a BeccaraP Faccioli
Mar 8, 2011·Journal of Chemical Theory and Computation·Judith B RommelJohannes Kästner
Aug 9, 2011·Journal of Chemical Theory and Computation·Alejandro Pérez, O Anatole von Lilienfeld

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Citations

Aug 10, 2013·The Journal of Chemical Physics·Hiroshi FujisakiAkinori Kidera
May 17, 2013·The Journal of Chemical Physics·Kimichi SuzukiMotoyuki Shiga

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