title: A quantum generalization of intrinsic reaction coordinate using path integral centroid coordinates.
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 the quantum effects even more drastically.
authors.affiliation: Center for Computational Science and E-systems, Japan Atomic Energy Agency, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8587, Japan.
authors.forename: Motoyuki
authors.initials: M
authors.lastname: Shiga
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Fujisaki
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D019281:Dimerization; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D011522:Protons; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D011522:Protons; D000641:Ammonia