Abstract
A computational study of the mechanisms and kinetics of the aqueous reactions of a hydrogen atom with haloacetates is presented. Several mechanisms in the close competition are observed, such as proton-coupled electron transfer (PCET), hydrogen atom transfer (HAT), and halogen abstraction (XA). Computations predict that dechlorination takes place via PCET mechanisms and not via XA, as stated earlier, while XA is the fastest mechanism for . The reaction rate constants are reasonably well predicted within the theoretically most reliable canonical variational transition state theory with small curvature tunneling corrections and compared with the experimental ones. To reproduce the experimental rate constants of the debromination process it is necessary to include the PCET and XA cumulative values. Small curvature tunneling corrections to the rate constants are the highest for HAT and PCET mechanisms, up to 70 times larger than the Wigner, while variational effects for XA mechanisms are very small.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: 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.
