Abstract
We have employed a flux-flux cross-correlation function approach (CCFA) to calculate quantum thermal rate constants of reactions for which an auto-correlation function approach (ACFA) is not adequate. In CCFA, two dividing surfaces partition a system into three regions, while in ACFA, two channels are defined by a dividing surface. Therefore, the CCFA method is appropriate for multi-channel reactions. In this paper, we show the efficiency of CCFA for multi-channel reactions. For example, we have examined self-diffusion of a hydrogen atom on a rigid Cu (111) surface. We introduce closed dividing surfaces that subdivide the potential energy surface for each channel. A combination of the closed dividing surfaces and CCFA allows us to calculate rate constants for both single and multi-hopping modes directly. Then, we calculate a diffusion constant without the usual uncorrelated hops approximation, using instead the calculated site-to-site hopping rates, thus showing the importance of multihops.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
More From: Journal of Theoretical and Computational Chemistry
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.