The Diabatic Picture of Electron Transfer, Reaction Barriers, and Molecular Dynamics
Top Cited Papers
Open Access
- 1 March 2010
- journal article
- Published by Annual Reviews in Annual Review of Physical Chemistry
- Vol. 61 (1), 149-170
- https://doi.org/10.1146/annurev.physchem.012809.103324
Abstract
Diabatic states have a long history in chemistry, beginning with early valence bond pictures of molecular bonding and extending through the construction of model potential energy surfaces to the modern proliferation of methods for computing these elusive states. In this review, we summarize the basic principles that define the diabatic basis and demonstrate how they can be applied in the specific context of constrained density functional theory. Using illustrative examples from electron transfer and chemical reactions, we show how the diabatic picture can be used to extract qualitative insight and quantitative predictions about energy landscapes. The review closes with a brief summary of the challenges and prospects for the further application of diabatic states in chemistry.Keywords
This publication has 127 references indexed in Scilit:
- On the Construction of Diabatic and Adiabatic Potential Energy Surfaces Based on Ab Initio Valence Bond TheoryThe Journal of Physical Chemistry A, 2008
- Hartree–Fock orbitals significantly improve the reaction barrier heights predicted by semilocal density functionalsThe Journal of Chemical Physics, 2008
- Predicting Exchange Coupling Constants in Frustrated Molecular Magnets Using Density Functional TheoryInorganic Chemistry, 2007
- On the Foundations of Chemical Reactivity TheoryThe Journal of Physical Chemistry A, 2007
- Gauge theory and quasidiabatic states in molecular physicsThe Journal of Chemical Physics, 1989
- Relation between the electron-transfer rate and the free energy change of reactionThe Journal of Physical Chemistry, 1989
- Electron transfers in chemistry and biologyBiochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, 1985
- Ab initio SCF calculations on electrostatically solvated molecules using a deformable three axes ellipsoidal cavityThe Journal of Chemical Physics, 1983
- Molecular Compounds and their Spectra. IIJournal of the American Chemical Society, 1952
- Electric Moments of Molecules in LiquidsJournal of the American Chemical Society, 1936