Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 143, Issue 12, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4931052
Keywords
-
Funding
- Deutsche Forschungsgemeinschaft [MA 1547/10, IV 171/2]
Ask authors/readers for more resources
With the goal of computing quantum free energy landscapes of reactive (bio) chemical systems in multi-dimensional space, we combine the metadynamics technique for sampling potential energy surfaces with the ab initio path integral approach to treating nuclear quantum motion. This unified method is applied to the double proton transfer process in the formic acid dimer (FAD), in order to study the nuclear quantum effects at finite temperatures without imposing a one-dimensional reaction coordinate or reducing the dimensionality. Importantly, the ab initio path integral metadynamics technique allows one to treat the hydrogen bonds and concomitant proton transfers in FAD strictly independently and thus provides direct access to the much discussed issue of whether the double proton transfer proceeds via a stepwise or concerted mechanism. The quantum free energy landscape we compute for this H-bonded molecular complex reveals that the two protons move in a concerted fashion from initial to product state, yet world-line analysis of the quantum correlations demonstrates that the protons are as quantum-uncorrelated at the transition state as they are when close to the equilibrium structure. (C) 2015 AIP Publishing LLC.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available