Help Privacy Policy Disclaimer
  Advanced SearchBrowse




Journal Article

Linear Energy Relationships in Ground State Proton Transfer and Excited State Proton-Coupled Electron Transfer


Hummer,  Gerhard       
Department of Theoretical Biophysics, Max Planck Institute of Biophysics, Max Planck Society;

External Resource
No external resources are shared
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available

Gamiz-Hernandez, A. P., Magomedov, A., Hummer, G., & Kaila, V. R. (2015). Linear Energy Relationships in Ground State Proton Transfer and Excited State Proton-Coupled Electron Transfer. The Journal of Physical Chemistry B, 119(6), 2611-2619. doi:10.1021/jp508790n.

Cite as: https://hdl.handle.net/11858/00-001M-0000-002A-47E2-7
Proton-coupled electron transfer (PCET) processes are elementary chemical reactions involved in a broad range of radical and redox reactions. Elucidating fundamental PCET reaction mechanisms are thus of central importance for chemical and biochemical research. Here we use quantum chemical density functional theory (DFT), time-dependent density functional theory (TDDFT), and the algebraic diagrammatic-construction through second-order (ADC(2)) to study the mechanism, thermodynamic driving force effects, and reaction barriers of both ground state proton transfer (pT) and photoinduced proton-coupled electron transfer (PCET) between nitrosylated phenyl-phenol compounds and hydrogen-bonded t-butylamine as an external base. We show that the obtained reaction barriers for the ground state pT reactions depend linearly on the thermodynamic driving force, with a Brønsted slope of 1 or 0. Photoexcitation leads to a PCET reaction, for which we find that the excited state reaction barrier depends on the thermodynamic driving force with a Brønsted slope of 1/2. To support the mechanistic picture arising from the static potential energy surfaces, we perform additional molecular dynamics simulations on the excited state energy surface, in which we observe a spontaneous PCET between the donor and the acceptor groups. Our findings suggest that a Brønsted analysis may distinguish the ground state pT and excited state PCET processes.