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

作者：Shiga Motoyuki^*; Fujisaki Hiroshi

来源：Journal of Chemical Physics, 2012, 136(18): 184103.

DOI：10.1063/1.4709723

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 NH3 molecule and N2H5- 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 NH3, 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 N2H5-, the centroid IRC is largely deviated from the "classical" IRC, and the free energy barrier is reduced by the quantum effects even more drastically.

• 出版日期2012-5-14