Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 120, Issue 2, Pages 299-305Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.5b10667
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Funding
- AFOSR [FA9550-12-1-0133]
- NSF [CBET-1150596]
- University of Washington
- Div Of Chem, Bioeng, Env, & Transp Sys
- Directorate For Engineering [1150596] Funding Source: National Science Foundation
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Herein, we demonstrate a convenient approach to systematically investigate chemical reaction dynamics using the metadynamics (MetaD) family of enhanced sampling methods. Using a symmetric S-N(2) reaction as a model system, we applied infrequent metadynamics, a theoretical framework based on acceleration factors, to quantitatively estimate the rate of reaction from biased and unbiased simulations. A systematic study of the algorithm and its application to chemical reactions was performed by sampling over 5000 independent reaction events. Additionally, we quantitatively reweighed exhaustive free-energy calculations to obtain the reaction potential-energy surface and showed that infrequent metadynamics works to effectively determine Arrhenius-like activation energies. Exact agreement with unbiased high-temperature kinetics is also shown. The feasibility of using the approach on actual ab initio molecular dynamics calculations is then presented by using Car-Parrinello MD+MetaD to sample the same reaction using only 10-20 calculations of the rare event. Owing to the ease of use and comparatively low-cost of computation, the approach has extensive potential applications for catalysis, combustion, pyrolysis, and enzymology.
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