← Back to Search

DOI: 10.1063/1.2360263

# Extracting Electron Transfer Coupling Elements From Constrained Density Functional Theory.

Qin Wu, T. Van Voorhis

Published 2006 · Chemistry, Medicine

Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (Hab) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculations on the Zn2+ and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the unconstrained DFT curve has no reaction barrier and gives Hab approximately 17 kcal/mol, which qualitatively disagrees with experimental results, the Hab calculated from constrained DFT is about 3 kcalmol and the generated ground state has a barrier height of 1.70 kcal/mol, successfully predicting (Q-TTF-Q)- to be a class II mixed-valence compound.

This paper references

10.1021/JA00299A017

Structure and redox properties of the water-oxidation catalyst [(bpy)2(OH2)RuORu(OH2)(bpy)2]4+

J. A. Gilbert (1985)

10.1016/0009-2614(93)87156-W

Use of approximate integrals in ab initio theory. An application in MP2 energy calculations

Martin W. Feyereisen (1993)

10.1016/0009-2614(93)90110-M

Direct construction of diabatic states in the CASSCF approach. Application to the conical intersection of the 1A2 and 1B1 excited states of ozone

W. Domcke (1993)

10.1063/1.1731961

Intramolecular Charge Transfer in Aromatic Free Radicals

H. Mcconnell (1961)

10.1039/DF9602900021

Exchange reactions and electron transfer reactions including isotopic exchange. Theory of oxidation-reduction reactions involving electron transfer. Part 4.—A statistical-mechanical basis for treating contributions from solvent, ligands, and inert salt

R. Marcus (1960)

10.1103/PHYSREV.97.1474

Quantum Theory of Many-Particle Systems. I. Physical Interpretations by Means of Density Matrices, Natural Spin-Orbitals, and Convergence Problems in the Method of Configurational Interaction

P. Loewdin (1955)

10.1021/JP026071X

Theoretical Investigation of the Ground and Excited States of Coumarin 151 and Coumarin 120

R. Cave (2002)

10.1063/1.1502255

Fragment charge difference method for estimating donor-acceptor electronic coupling: Application to DNA π-stacks

A. Voityuk (2002)

10.1016/0009-2614(95)01310-5

Generalization of the Mulliken-Hush treatment for the calculation of electron transfer matrix elements

R. Cave (1996)

10.1007/S002140100250

Electronic excitation of sulfur-organic compounds – performance of time-dependent density functional theory

Jürgen Fabian (2001)

10.1063/1.474023

Calculation of electronic coupling matrix elements for ground and excited state electron transfer reactions: Comparison of the generalized Mulliken-Hush and block diagonalization methods

R. Cave (1997)

10.1002/9780470166093.CH7

Intervalence‐Transfer Absorption. Part 2. Theoretical Considerations and Spectroscopic Data

N. Hush (2007)

10.1073/PNAS.0504046102

Molecular electronics

C. Joachim (2005)

10.1021/CR040084K

Charge-transfer and energy-transfer processes in pi-conjugated oligomers and polymers: a molecular picture.

J. Brédas (2004)

10.1021/JP061848Y

Direct calculation of electron transfer parameters through constrained density functional theory.

Qin Wu (2006)

10.1063/1.1696792

On the Theory of Electron-Transfer Reactions. VI. Unified Treatment for Homogeneous and Electrode Reactions

R. Marcus (1965)

10.1021/J100357A005

Relation between the electron-transfer rate and the free energy change of reaction

M. Tachiya (1989)

10.1021/JA00237A007

Estimation of inner shell Marcus terms for amino nitrogen compounds by molecular orbital calculations

S. F. Nelsen (1987)

10.1021/JP9605663

Contemporary Issues in Electron Transfer Research

P. Barbara (1996)

10.1063/1.1673095

Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms

A. J. H. Wachters (1970)

10.1063/1.2166233

First-principles density-functional theory calculations of electron-transfer rates in azurin dimers.

A. Migliore (2006)

10.1103/PHYSREVLETT.52.997

Density-Functional Theory for Time-Dependent Systems

Erich Runge (1984)

10.1021/CT0503163

Constrained Density Functional Theory and Its Application in Long-Range Electron Transfer.

Qin Wu and (2006)

10.1103/RevModPhys.65.599

Electron transfer reactions in chemistry. Theory and experiment

R. Marcus (1993)

10.1063/1.1742723

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I

R. Marcus (1956)

10.1142/9789812830586_0005

Time-Dependent Density Functional Response Theory for Molecules

M. E. Casida (1995)

10.1063/1.1904586

Time-dependent density functional theory: past, present, and future.

K. Burke (2005)

10.1016/S0065-2792(08)60179-X

Mixed Valence Chemistry-A Survey and Classification

M. Robin (1968)

10.1063/1.464913

Density-functional thermochemistry. III. The role of exact exchange

Axel D. Becke (1993)

10.1103/PHYSREVLETT.53.2512

Ground States of Constrained Systems: Application to Cerium Impurities

P. Dederichs (1984)

10.1103/PHYSREVA.38.3098

Density-functional exchange-energy approximation with correct asymptotic behavior.

Becke (1988)

10.1103/PHYSREVA.72.024502

Direct optimization method to study constrained systems within density-functional theory

Qin Wu (2005)

10.1063/1.480117

Perturbed ground state method for electron transfer

O. Prezhdo (1999)

10.1103/PHYSREVB.37.785

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.

Lee (1988)

10.1021/JA00237A013

Microscopic examination of free-energy relationships for electron transfer in polar solvents

Jenn-Kang Hwang (1987)

10.1103/PHYSREV.136.B864

THE INHOMOGENEOUS ELECTRON GAS.

P. Hohenberg (1964)

10.1021/CR0505627

Single-reference ab initio methods for the calculation of excited states of large molecules.

A. Dreuw (2005)

10.1016/S0009-2614(98)00862-8

RI-MP2: optimized auxiliary basis sets and demonstration of efficiency

F. Weigend (1998)

10.1007/978-94-009-9027-2_2

Density-functional theory of atoms and molecules

R. Parr (1989)

10.1016/S0301-0104(03)00388-4

Ab initio study of the excited-state coupled electron proton-transfer process in the 2-aminopyridine dimer

A. L. Sobolewski (2003)

10.1021/JA01123A067

Molecular Compounds and their Spectra. II

R. S. Mulliken (1952)

10.1103/PhysRevLett.94.036104

Dissociation of O2 at Al(111): the role of spin selection rules.

J. Behler (2005)

10.1063/1.457323

Gauge theory and quasidiabatic states in molecular physics

T. Pacher (1989)

10.1103/PHYSREVB.56.16021

Comment on ``Significance of the highest occupied Kohn-Sham eigenvalue''

J. Perdew (1997)

10.1021/AR00148A005

Long-distance electron transfer in proteins and model systems

G. Mclendon (1988)

10.1039/B101377G

Long-distance intervalence electron transfer

J. Launay (2001)

10.1021/CR00005A007

Quantum chemical probes of electron-transfer kinetics: the nature of donor-acceptor interactions

M. D. Newton (1991)

10.1021/J100375A024

Bridge-assisted electron transfer: effective electronic coupling

M. Ratner (1990)

10.1103/PHYSREV.140.A1133

Self-Consistent Equations Including Exchange and Correlation Effects

W. Kohn (1965)

10.1002/ANIE.200250587

Intramolecular electron transfer mediated by a tetrathiafulvalene bridge in a purely organic mixed-valence system.

N. Gautier (2003)

10.1016/0304-4173(85)90014-X

Electron transfers in chemistry and biology

R. Marcus (1985)

10.1021/JA053710J

cis,cis-[(bpy)2RuVO]2O4+ catalyzes water oxidation formally via in situ generation of radicaloid RuIV-O*.

Xiaofan Yang (2006)

10.1063/1.2145878

Accurate magnetic exchange couplings in transition-metal complexes from constrained density-functional theory.

I. Rudra (2006)

10.1021/CR00011A003

Analysis of the interactions responsible for long-range through-bond-mediated electronic coupling between remote chromophores attached to rigid polynorbornyl bridges

K. Jordan (1992)

10.1007/BF01112569

Density matrix averaged atomic natural orbital (ANO) basis sets for correlated molecular wave functions

Per-Olof Widmark (1990)

10.1021/JA039556N

Failure of time-dependent density functional theory for long-range charge-transfer excited states: the zincbacteriochlorin-bacteriochlorin and bacteriochlorophyll-spheroidene complexes.

A. Dreuw (2004)

10.1142/2914

Recent Advances in Density Functional Methods Part III

D. P. Chong (2002)

10.1063/1.456153

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen

T. H. Dunning (1989)

10.1063/1.476859

A challenge for density functionals: Self-interaction error increases for systems with a noninteger number of electrons

Y. Zhang (1998)

10.1021/JP001271Z

Testing the Condon Approximation for Electron Transfer via the Mulliken−Hush Model

Mohamad Toutounji (2000)

10.1021/JP0404596

What is an atom in a molecule?

R. Parr (2005)

10.1063/1.2179072

Self-interaction-free exchange-correlation functional for thermochemistry and kinetics.

P. Mori-Sánchez (2006)

10.1063/1.1590951

Long-range charge-transfer excited states in time-dependent density functional theory require non-local exchange

A. Dreuw (2003)

10.1021/JA00404A010

Electron transfer in chemical and biological systems. Orbital rules for nonadiabatic transfer

S. Larsson (1981)

This paper is referenced by

10.1063/5.0023609

Photoinduced charge transfer in Zn(II) and Au(III)-ligated symmetric and asymmetric bacteriochlorin dyads: A computational study.

H. Aksu (2020)

10.1021/ja807590q

Enhanced intersystem crossing in three-spin systems: a perturbation theory treatment.

S. Yeganeh (2009)

10.1002/wcms.1290

Challenges in large scale quantum mechanical calculations

L. Ratcliff (2016)

10.1021/acs.chemrev.7b00086

Charge Transport in Molecular Materials: An Assessment of Computational Methods.

H. Oberhofer (2017)

10.1021/ct2008318

Block-Localized Wavefunction (BLW) Based Two-State Approach for Charge Transfers between Phenyl Rings.

Y. Mo (2012)

Taking control of charge transfer : strategic design for solar cells

Adriano Monti (2015)

10.1021/ct400618k

Electron Transfer in Electrophilic Aromatic Nitration and Nitrosation: Computational Evidence for the Marcus Inverted Region.

Zhenhua Chen (2013)

10.1021/ct2003463

Prediction of Charge Mobility in Amorphous Organic Materials through the Application of Hopping Theory.

C. Lee (2011)

10.1098/rsta.2007.2148

Probing the localized-to-delocalized transition

Javier J Concepcion (2007)

10.1021/JP304433T

Triplet vs Singlet Energy Transfer in Organic Semiconductors: The Tortoise and the Hare

S. Yost (2012)

10.1021/ACS.JPCC.7B05522

What Is the Optoelectronic Effect of the Capsule on the Guest Molecule in Aqueous Host/Guest Complexes? A Combined Computational and Spectroscopic Perspective

S. Bhandari (2017)

10.1021/ACS.CHEMMATER.7B04618

Adiabatic and Nonadiabatic Charge Transport in Li–S Batteries

H. Park (2018)

Density functional theory studies of surface interactions and electron transfer in porphyrins and other molecules

A. M. P. Sena (2010)

10.1002/cphc.201300085

First-principles investigation of anisotropic electron and hole mobility in heterocyclic oligomer crystals.

J. Huang (2013)

10.1021/jp204585s

Electron localization function study on intramolecular electron transfer in the QTTFQ and DBTTFI radical anions.

J. Kalinowski (2011)

Identi fi cation of oxide defects in semiconductor devices : A systematic approach linking DFT to rate equations and experimental evidence

W. Goesa (2018)

10.1007/978-90-481-2596-8_15

Orbital-Free Embedding Effective Potential in Analytically Solvable Cases

A. Savin (2009)

10.1021/ct900024f

DFT Calculations on Charge-Transfer States of a Carotenoid-Porphyrin-C60 Molecular Triad.

T. Baruah (2009)

10.1063/1.3666005

Modelling charge transfer reactions with the frozen density embedding formalism.

M. Pavanello (2011)

10.1021/acs.jctc.7b00362

Constrained-Orbital Density Functional Theory. Computational Method and Applications to Surface Chemical Processes.

Craig P Plaisance (2017)

10.1021/jp504418c

Functional Mode Electron-Transfer Theory.

H. Chen (2014)

10.1021/JP205262U

Time-Dependent Theory of the Rate of Photo-induced Electron Transfer

H. Chen (2011)

10.1063/1.3125436

Nonadiabatic dynamics at metal surfaces: independent-electron surface hopping.

N. Shenvi (2009)

Constrained Density-Functional Theory--Configuration Interaction

Benjamin Kaduk (2012)

10.1088/0034-4885/75/9/096402

Experimental and theoretical studies of plasmon-molecule interactions.

H. Chen (2012)

10.1021/JP2047085

Effects of Charge Localization on the Orbital Energies of Bithiophene Clusters

T. A. Madison (2011)

10.1063/1.4922378

Fragment approach to constrained density functional theory calculations using Daubechies wavelets.

L. Ratcliff (2015)

10.1021/jp508337x

Molecular excited states: accurate calculation of relative energies and electronic coupling between charge transfer and non-charge transfer states.

Brad S. Veldkamp (2015)

10.1002/jcc.25234

Electronic and structural properties of Lin@Be2B8 (n = 1–14) and Lin@Be2B36 (n = 1–21) nanoflakes shed light on possible anode materials for Li‐based batteries

Moein Goodarzi (2018)

10.1021/ar5002796

Electron transfer, decoherence, and protein dynamics: insights from atomistic simulations.

Christophe Narth (2015)

10.1063/1.4722552

Constrained spin-density dynamics of an iron-sulfur complex: ferredoxin cofactor.

M. E. Ali (2012)

10.1039/c2cp40222j

Hybrid one-electron/many-electron methods for ionized states of molecular clusters.

J. Zhang (2012)

See more