The diabatic picture of electron transfer, reaction barriers, and molecular dynamics.
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.
Van Voorhis
Troy
T
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA. tvan@mit.edu
Kowalczyk
Tim
T
Kaduk
Benjamin
B
Wang
Lee-Ping
LP
Cheng
Chiao-Lun
CL
Wu
Qin
Q