Diabatic Potential Energy Surfaces for Charge‐Transfer Processes

Sidis, V.

doi:10.1002/9780470141403.ch2

Cited by 83 publications

(18 citation statements)

References 145 publications

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“…The charge transfer integral or effective electronic coupling between electron (or hole) donor and acceptor groups is a key parameter that controls the rate of electron transfer (ET) as well as electronic excitation energy transfer. , In most theoretical methods, a prerequisite for computing transfer integrals is a suitable definition of the electronically localized donor and acceptor configurations, called diabatic states, which distinguish the initial and final locations of the charge or excitation . Because diabatic states are not uniquely defined, − a plethora of techniques have been developed to model diabatic configurations ,− and the corresponding charge transfer matrix elements . Broadly speaking, methods for constructing diabatic states may be grouped into two categories; the first relies on a suitable transformation of the relevant adiabatic states to produce localized orbitals to form the corresponding diabatic states, and the second approach determines diabatic states on the basis of the characteristic local features of the physical system as in valence bond theory .…”

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confidence: 99%

Multistate Density Functional Theory for Effective Diabatic Electronic Coupling

Ren

Provorse

Bao

et al. 2016

J. Phys. Chem. Lett.

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Multistate density functional theory (MSDFT) is presented to estimate the effective transfer integral associated with electron and hole transfer reactions. In this approach, the charge-localized diabatic states are defined by block localization of Kohn–Sham orbitals, which constrain the electron density for each diabatic state in orbital space. This differs from the procedure used in constrained density functional theory that partitions the density within specific spatial regions. For a series of model systems, the computed transfer integrals are consistent with experimental data and show the expected exponential attenuation with the donor–acceptor separation. The present method can be used to model charge transfer reactions including processes involving coupled electron and proton transfer.

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confidence: 99%

Multistate Density Functional Theory for Effective Diabatic Electronic Coupling

Ren

Provorse

Bao

et al. 2016

J. Phys. Chem. Lett.

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“…Finally, diabatic states play a qualitative role in our understanding of molecular bonding [15][16][17] (as illustrated by the NaCl example above), electron transfer [18,19] and proton tunnelling [20][21][22] This review article is intended as an introduction the basic concepts about how diabatic states are constructed and how they are used to describe chemical phenomena. After a summary of different definitions of diabatic states -and in particular why so many competing definitions exist -we focus on a particular definition based on constrained density functional theory (CDFT).…”

Section: Introductionmentioning

confidence: 99%

The Diabatic Picture of Electron Transfer, Reaction Barriers, and Molecular Dynamics

Voorhis

Kowalczyk

Kaduk

et al. 2010

Annu. Rev. Phys. Chem.

298

366

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Diabatic states have a long history in chemistry, beginning with early valence bond pictures of molecular bonding and stretching 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 resumé of the challenges and prospects for the further application of diabatic states in chemistry.

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“…Diabatic states [10][11][12][13](including valence bond states) are a powerful tool for developing chemical concepts [14], including understanding and describing conical intersections [15], and going beyond the Born-Oppenheimer approximation [16]. Previously it has been proposed that hydrogen bonding and hydrogen transfer reactions can be described by Empirical Valence Bond models [17] where the diabatic states are valence bond states.…”

Section: A Reduced Hilbert Space For the Effective Hamiltonianmentioning

confidence: 99%

A diabatic state model for double proton transfer in hydrogen bonded complexes

McKenzie

2014

The Journal of Chemical Physics

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Four diabatic states are used to construct a simple model for double proton transfer in hydrogen bonded complexes. Key parameters in the model are the proton donor-acceptor separation R and the ratio, D 1 /D 2 , between the proton affinity of a donor with one and two protons. Depending on the values of these two parameters the model describes four qualitatively different ground state potential energy surfaces, having zero, one, two, or four saddle points. In the limit D 2 = D 1 the model reduces to two decoupled hydrogen bonds.As R decreases a transition can occur from a concerted to a sequential mechanism for double proton transfer. *

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Diabatic Potential Energy Surfaces for Charge‐Transfer Processes

Cited by 83 publications

References 145 publications

Multistate Density Functional Theory for Effective Diabatic Electronic Coupling

Multistate Density Functional Theory for Effective Diabatic Electronic Coupling

The Diabatic Picture of Electron Transfer, Reaction Barriers, and Molecular Dynamics

A diabatic state model for double proton transfer in hydrogen bonded complexes

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