Abstract
Quantum mechanical and semiclassical formulations of nonadiabatic electron transfer theory are usually implemented within a Born–Oppenheimer regime. Calculations on real weakly interacting systems are so difficult that this approximation is rarely questioned. The Born–Oppenheimer approximation becomes qualitatively wrong for electron transfers at very large distances. A model vibronic problem is exactly solved and compared with the Born–Oppenheimer result. Rate expressions are derived from the wave functions using the ‘‘golden rule’’ approximation. Electron propagation is intimately correlated to nuclear motion so that the vibrational energy left on the donor critically affects the electronic decay length. Several deviations from the usual predictions appear for transfers over very large distances.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
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.