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