Abstract
Nuclear quantum effects on proton transfer and reorientation in is investigated theoretically using the ab initio path-integral molecular-dynamics simulation technique. The result demonstrates that adding quantum fluctuations has a large effect on, in particular, the transfer barrier. The corresponding rates and diffusion coefficient are evaluated using the path-centroid transition state theory. In contrast with what is found assuming classical mechanics for the nuclear motion, the reorientation step becomes rate limiting below 600 K.
- Received 18 June 2008
DOI:https://doi.org/10.1103/PhysRevLett.101.215902
©2008 American Physical Society