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Introducing The Mean Field Approximation To CDFT/MMpol Method: Statistically Converged Equilibrium And Nonequilibrium Free Energy Calculation For Electron Transfer Reactions In Condensed Phases.
H. Nakano, H. Sato
Published 2017 · Physics, Medicine
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A new theoretical method to study electron transfer reactions in condensed phases is proposed by introducing the mean-field approximation into the constrained density functional theory/molecular mechanical method with a polarizable force field (CDFT/MMpol). The method enables us to efficiently calculate the statistically converged equilibrium and nonequilibrium free energies for diabatic states in an electron transfer reaction by virtue of the mean field approximation that drastically reduces the number of CDFT calculations. We apply the method to the system of a formanilide-anthraquinone dyad in dimethylsulfoxide, in which charge recombination and cis-trans isomerization reactions can take place, previously studied by the CDFT/MMpol method. Quantitative agreement of the driving force and the reorganization energy between our results and those from the CDFT/MMpol calculation and the experimental estimates supports the utility of our method. The calculated nonequilibrium free energy is analyzed by its decomposition into several contributions such as those from the averaged solute-solvent electrostatic interactions and the explicit solvent electronic polarization. The former contribution is qualitatively well described by a model composed of a coarse-grained dyad in a solution in the linear response regime. The latter contribution reduces the reorganization energy by more than 10 kcal/mol.
This paper references
Configuration interaction based on constrained density functional theory: a multireference method.
Qin Wu (2007)
Fragment-based Quantum Mechanical/Molecular Mechanical Simulations of Thermodynamic and Kinetic Process of the Ru2+-Ru3+ Self-Exchange Electron Transfer.
X. Zeng (2012)
Generalization of the Mulliken-Hush treatment for the calculation of electron transfer matrix elements
R. Cave (1996)
Equilibrium and nonequilibrium solvation and solute electronic structure. III. Quantum theory
H. Kim (1992)
Proton-coupled electron transfer in molecular electrocatalysis: theoretical methods and design principles.
Brian H. Solis (2014)
Ab Initio Molecular Orbital Theory on Intramolecular Charge Polarization: Effect of Hydrogen Abstraction on the Charge Sensitivity of Aromatic and Nonaromatic Species
Akihiro Morita and (1997)
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
R. Marcus (1956)
Variational calculation of quantum mechanical/molecular mechanical free energy with electronic polarization of solvent.
H. Nakano (2012)
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)
Magnetic exchange couplings from constrained density functional theory: an efficient approach utilizing analytic derivatives.
J. Phillips (2011)
Simulating molecular conductance using real-time density functional theory
Chiao-Lun Cheng (2006)
Molecular dynamics simulation with the charge response kernel: Diffusion dynamics of pyrazine and pyrazinyl radical in methanol
A. Morita (1998)
Extension of Marcus picture for electron transfer reactions with large solvation changes.
R. Vuilleumier (2012)
Supercell convergence of charge-transfer energies in pentacene molecular crystals from constrained DFT
David H. P. Turban (2016)
Theoretical calculation of reorganization energy for electron self-exchange reaction by constrained density functional theory and constrained equilibrium thermodynamics.
H. Ren (2013)
Recent Advances in the Theory and Molecular Simulation of Biological Electron Transfer Reactions.
J. Blumberger (2015)
Polarizability of the active site of cytochrome c reduces the activation barrier for electron transfer
M. Dinpajooh (2016)
Switching in molecular transport junctions: polarization response.
S. Yeganeh (2007)
Quantum mechanics/molecular mechanics minimum free-energy path for accurate reaction energetics in solution and enzymes: sequential sampling and optimization on the potential of mean force surface.
H. Hu (2008)
An all-atom simulation study on intermolecular interaction of DMSO–water system
Yi Lei (2003)
Computation of the reduction free energy of coenzyme in aqueous solution by the QM/MM-ER method
H. Takahashi (2008)
Analytical energy gradient for the reference interaction site model multiconfigurational self‐consistent‐field method: Application to 1,2‐difluoroethylene in aqueous solution
H. Sato (1996)
Hydration free energy and potential of mean force for a model of the sodium chloride ion pair in supercritical water with ab initio solute–solvent interactions
W. Liu (2003)
Robust and Efficient Constrained DFT Molecular Dynamics Approach for Biochemical Modeling.
J. Řezáč (2012)
Polarizable solute in polarizable and flexible solvents: simulation study of electron transfer reaction systems.
T. Ishida (2005)
Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. I
R. Marcus (1956)
A combined quantum mechanical and molecular mechanical potential for molecular dynamics simulations
M. Field (1990)
A double-QM/MM method for investigating donor-acceptor electron-transfer reactions in solution.
Z. Futera (2014)
A wave-function based approach for polarizable charge model: Systematic comparison of polarization effects on protic, aprotic, and ionic liquids.
H. Nakano (2010)
Quantifying charge transfer energies at donor-acceptor interfaces in small-molecule solar cells with constrained DFTB and spectroscopic methods.
R. Scholz (2013)
Electron Transfer Reactions in Condensed Phases
M. Newton (1984)
Theoretical Study on Electronic and Solvent Reorganization Associated with a Charging Process of Organic Compounds. 2. A New Decomposition Procedure into Electrostatic and Nonelectrostatic Responses
H. Sato (2004)
Adiabatic and diabatic representations for atom-molecule collisions: Treatment of the collinear arrangement
M. Baer (1975)
Constructing diabatic states from adiabatic states: extending generalized Mulliken-Hush to multiple charge centers with boys localization.
Joseph E Subotnik (2008)
Diabatic CASSCF orbitals and wavefunctions
W. Domcke (1994)
Auger-assisted electron transfer from photoexcited semiconductor quantum dots.
Haiming Zhu (2014)
Quantum effects in biological electron transfer.
A. de la Lande (2012)
The diabatic picture of electron transfer, reaction barriers, and molecular dynamics.
T. Van Voorhis (2010)
Free energies for biological electron transfer from QM/MM calculation: method, application and critical assessment.
J. Blumberger (2008)
Variational and perturbative formulations of quantum mechanical/molecular mechanical free energy with mean-field embedding and its analytical gradients.
T. Yamamoto (2008)
A hybrid approach to simulation of electron transfer in complex molecular systems
T. Kubař (2013)
Including charge penetration effects into the ESP derived partial charge operator
H. Nakano (2012)
Solvent Reorganization and Donor/Acceptor Coupling in Electron-Transfer Processes: Self-Consistent Reaction Field Theory and ab Initio Applications
Y. Liu (1995)
Computational study of bridge-assisted intervalence electron transfer.
F. Ding (2010)
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)
Accelerating QM/MM free energy calculations: representing the surroundings by an updated mean charge distribution.
E. Rosta (2008)
Modeling Charge Resonance in Cationic Molecular Clusters: Combining DFT-Tight Binding with Configuration Interaction.
M. Rapacioli (2011)
Ab initio calculation of proton-coupled electron transfer rates using the external-potential representation: a ubiquinol complex in solution.
T. Yamamoto (2007)
Development and testing of a general amber force field
J. Wang (2004)
pKa calculations in solution and proteins with QM/MM free energy perturbation simulations: a quantitative test of QM/MM protocols.
D. Riccardi (2005)
Ab initio study of the emissive charge-transfer states of solvated chromophore-functionalized silsesquioxanes.
S. Zheng (2012)
Model space diabatization for quantum photochemistry.
S. Li (2015)
Constrained density functional theory.
Benjamin Kaduk (2012)
A stable fluctuating-charge polarizable model for molecular dynamics simulations: Application to aqueous electron transfers
Koji Ando (2001)
Simulation of the dynamics of electron transfer reactions in polar solvents: Semiclassical trajectories and dispersed polaron approaches
A. Warshel (1986)
Drastic difference in lifetimes of the charge-separated state of the formanilide-anthraquinone dyad versus the ferrocene-formanilide-anthraquinone triad and their photoelectrochemical properties of the composite films with fullerene clusters.
K. Okamoto (2005)
A brief history of molecular electronics.
M. Ratner (2013)
Electron transfer reactions in chemistry. Theory and experiment
R. Marcus (1993)
Ultrafast intersystem crossing in 9,10-anthraquinones and intramolecular charge separation in an anthraquinone-based dyad.
H. J. V. Ramesdonk (2006)
Triplet Excitation Energy Transfer with Constrained Density Functional Theory
S. Yeganeh (2010)
Quasidiabatic states from ab initio calculations by block diagonalization of the electronic Hamiltonian: Use of frozen orbitals
T. Pacher (1991)
Electronic non-adiabatic transitions derivation of the general adiabatic-diabatic transformation matrix
M. Baer (1980)
Charge transport across insulating self-assembled monolayers: non-equilibrium approaches and modeling to relate current and molecular structure.
F. Mirjani (2014)
Electron transfer in peptides.
A. Shah (2015)
Direct calculation of electron transfer parameters through constrained density functional theory.
Qin Wu (2006)
Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries
Kevin Leung (2012)
Reorganization free energies for long-range electron transfer in a porphyrin-binding four-helix bundle protein.
J. Blumberger (2006)
Diabatization Schemes for Generating Charge-Localized Electron-Proton Vibronic States in Proton-Coupled Electron Transfer Systems.
Andrew Sirjoosingh (2011)
A study of the diabatic electronic representation within the Born-Oppenheimer approximation
M. Baer (1992)
Theoretical studies of enzymic reactions: dielectric, electrostatic and steric stabilization of the carbonium ion in the reaction of lysozyme.
A. Warshel (1976)
Marcus-Hush-Chidsey theory of electron transfer applied to voltammetry: A review
Martin C. Henstridge (2012)
Computer simulations of electron-transfer reactions in solution and in photosynthetic reaction centers.
A. Warshel (1991)
Chemical Dynamics in Condensed Phases: Relaxation, Transfer, and Reactions in Condensed Molecular Systems
A. Nitzan (2006)
Electron transfer rates from time-dependent correlation functions. Wavepacket dynamics, solvent effects, and applications
M. D. Todd (1994)
Effect of electronic polarization on charge-transport parameters in molecular organic semiconductors.
E. Valeev (2006)
Equilibrium and Nonequilibrium Solvation Structure of Hexaammineruthenium (II, III) in Aqueous Solution: Ab Initio RISM-SCF Study†
H. Sato (2002)
Nonequilibrium Oscillatory Electron Transfer in Bacterial Photosynthesis
Koji Ando (1998)
Multi-Scale Approach to Non-Adiabatic Charge Transport in High-Mobility Organic Semiconductors.
Alexander Heck (2015)
Electronic couplings for molecular charge transfer: benchmarking CDFT, FODFT, and FODFTB against high-level ab initio calculations.
A. Kubas (2014)
A priori evaluation of aqueous polarization effects through Monte Carlo QM-MM simulations.
J. Gao (1992)
Electron transfer : from isolated molecules to biomolecules
M. Bixon (2007)
Electron transport in molecular junctions
N. Tao (2006)
Reference interaction site model self-consistent field study for solvation effect on carbonyl compounds in aqueous solution
S. Ten-no (1994)
Solvent control of spin-dependent charge recombination mechanisms within donor-conjugated bridge-acceptor molecules.
E. Weiss (2004)
Extension of the fourfold way for calculation of global diabatic potential energy surfaces of complex, multiarrangement, non-Born–Oppenheimer systems: Application to HNCO(S0,S1)
H. Nakamura (2003)
General atomic and molecular electronic structure system
M. Schmidt (1993)
The initial and final states of electron and energy transfer processes: diabatization as motivated by system-solvent interactions.
Joseph E Subotnik (2009)
On the construction of diabatic and adiabatic potential energy surfaces based on ab initio valence bond theory.
Lingchun Song (2008)
Valence bond theory for chemical dynamics
D. Truhlar (2007)
Communication: Conical intersections using constrained density functional theory-configuration interaction.
Benjamin Kaduk (2010)
Electronic properties of disordered organic semiconductors via QM/MM simulations.
S. Difley (2010)
Efficient algorithms for the simulation of non-adiabatic electron transfer in complex molecular systems: application to DNA.
T. Kubař (2013)
Contemporary Issues in Electron Transfer Research
P. Barbara (1996)
Multiscale Free Energy Simulations: An Efficient Method for Connecting Classical MD Simulations to QM or QM/MM Free Energies Using Non-Boltzmann Bennett Reweighting Schemes
G. König (2014)
Hybrid QM/MM Potentials of Mean Force with Interpolated Corrections
J. Ruiz-Pernía (2004)
Quantum mechanical free energy barrier for an enzymatic reaction.
T. H. Rod (2005)
Solvent‐Fluctuation Control of Solution Reactions and its Manifestation in Protein Functions
H. Sumi (2007)
QM/MM Study of Photoinduced Reduction of a Tetrahedral Ag20+ Cluster by a Ag Atom
H. Chen (2014)
Molecular Insight Into the Energy Levels at the Organic Donor/Acceptor Interface: A Quantum Mechanics/Molecular Mechanics Study
S. Yost (2011)
Fragment approach to constrained density functional theory calculations using Daubechies wavelets.
L. Ratcliff (2015)
A quantum chemical determination of diabatic states
K. Ruedenberg (1993)
Simulation of solution phase electron transfer in a compact donor-acceptor dyad.
T. Kowalczyk (2011)
Approximately diabatic states from block diagonalization of the electronic Hamiltonian
T. Pacher (1988)
Role of solvent electronic polarization in electron-transfer processes
H. Kim (1990)
Electrochemical Solvent Reorganization Energies in the Framework of the Polarizable Continuum Model.
S. Ghosh (2014)
Calculation from First Principles of Intramolecular Golden-Rule Rate Constants for Photo-Induced Electron Transfer in Molecular Donor–Acceptor Systems
M. Lee (2013)
Quasi-diabatic States from Active Space Decomposition.
Shane M Parker (2014)
PROPOSAL AND NUMERICAL TEST OF A SIMPLE DIABATIZATION SCHEME
A. Thiel (1999)
Toward Fast and Accurate Evaluation of Charge On-Site Energies and Transfer Integrals in Supramolecular Architectures Using Linear Constrained Density Functional Theory (CDFT)-Based Methods.
L. Ratcliff (2015)
Constrained density functional theory applied to electron tunnelling between defects in MgO.
J. Blumberger (2013)
Time-Dependent Theory of the Rate of Photo-induced Electron Transfer
H. Chen (2011)
Electron transfer, decoherence, and protein dynamics: insights from atomistic simulations.
Christophe Narth (2015)
Crossover from incoherent to coherent electron tunneling between defects in MgO
K. P. McKenna (2012)
Free energies of chemical reactions in solution and in enzymes with ab initio quantum mechanics/molecular mechanics methods.
H. Hu (2008)
Ground States of Constrained Systems: Application to Cerium Impurities
P. Dederichs (1984)
Quantum-mechanical calculations of solvation free energies. A combined ab initio pseudopotential free-energy perturbation approach
N. Vaidehi (1992)
Determination of diabatic states through enforcement of configurational uniformity
G. J. Atchity (1997)
Reorganization energy for internal electron transfer in multicopper oxidases.
L. Hu (2011)
Condensed phase electron transfer beyond the Condon approximation.
M. G. Mavros (2016)
Paradynamics: an effective and reliable model for ab initio QM/MM free-energy calculations and related tasks.
N. Plotnikov (2011)
QUANTUM ENERGY GAP LAW OF OUTER-SPHERE ELECTRON TRANSFER REACTIONS : A MOLECULAR DYNAMICS STUDY ON AQUEOUS SOLUTION
Koji Ando (1997)
Electron Tunneling in Solid-State Electron-Transfer Reactions
K. Mikkelsen (1987)
Analytic energy gradients for constrained DFT-configuration interaction.
Benjamin Kaduk (2014)
Optimal diabatic states based on solvation parameters.
Ethan C Alguire (2012)
Spin-charge separation in molecular wire conductance simulations
J. S. Evans (2008)
Biochemistry and Theory of Proton-Coupled Electron Transfer
A. Migliore (2014)
The direct calculation of diabatic states based on configurational uniformity
H. Nakamura (2001)
Electron Transport in Molecular Wire Junctions
A. Nitzan (2003)
Theoretical study of electronic and solvent reorganization associated with a charging process of organic compounds. I. Molecular and atomic level description of solvent reorganization
H. Sato (2003)
A well-behaved electrostatic potential-based method using charge restraints for deriving atomic char
Christian Baily (1993)
Electronic coupling matrix elements from charge constrained density functional theory calculations using a plane wave basis set.
H. Oberhofer (2010)
Solvated Charge Transfer States of Functionalized Anthracene and Tetracyanoethylene Dimers: A Computational Study Based on a Range Separated Hybrid Functional and Charge Constrained Self-Consistent Field with Switching Gaussian Polarized Continuum Models.
Shaohui Zheng (2013)
Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye-Semiconductor Interface.
K. Siefermann (2014)
An Ab Initio QM/MM-Based Approach to Efficiently Evaluate Vertical Excitation Energies in Condensed Phases Including the Nonequilibrium Solvation Effect.
H. Nakano (2016)
An ab initio molecular orbital-valence bond (MOVB) method for simulating chemical reactions in solution
Y. Mo (2000)
Direct diabatization of electronic states by the fourfold way. II. Dynamical correlation and rearrangement processes
H. Nakamura (2002)
Combined Electrostatically Embedded Multiconfiguration Molecular Mechanics and Molecular Mechanical Method: Application to Molecular Dynamics Simulation of a Chemical Reaction in Aqueous Solution with Hybrid Density Functional Theory.
Masahiro Higashi (2008)
Free-energy surfaces for liquid-phase reactions and their use to study the border between concerted and nonconcerted alpha,beta-elimination reactions of esters and thioesters.
Younghee Kim (2010)
Electron transfers in chemistry and biology
R. Marcus (1985)
Relation between the electron-transfer rate and the free energy change of reaction
M. Tachiya (1989)
Implementation of Constrained DFT for Computing Charge Transfer Rates within the Projector Augmented Wave Method.
Marko M Melander (2016)
Solvent Reorganization Energy of Charge Transfer in DNA Hairpins
David N. LeBard (2003)
Validity of describing reaction coordinate of intramolecular charge transfer of 1,3-dinitrobenzene anion radical using constrained density functional theory
T. Ogawa (2011)
Using atomic layer deposition to hinder solvent decomposition in lithium ion batteries: first-principles modeling and experimental studies.
Kevin Leung (2011)
Charge constrained density functional molecular dynamics for simulation of condensed phase electron transfer reactions.
H. Oberhofer (2009)
Gauge theory and quasidiabatic states in molecular physics
T. Pacher (1989)
Using a classical potential as an efficient importance function for sampling from an ab initio potential
R. Iftimie (2000)
Reorganization free energies and quantum corrections for a model electron self-exchange reaction: comparison of polarizable and non-polarizable solvent models
J. Blumberger (2008)
Progress in ab initio QM/MM free-energy simulations of electrostatic energies in proteins: accelerated QM/MM studies of pKa, redox reactions and solvation free energies.
S. C. Kamerlin (2009)
QM/MM Reweighting Free Energy SCF for Geometry Optimization on Extensive Free Energy Surface of Enzymatic Reaction.
Takahiro Kosugi (2012)
Recent advances in QM/MM free energy calculations using reference potentials☆
F. Duarte (2015)
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)
Electrochemical charge transfer at a metallic electrode: a simulation study.
S. K. Reed (2008)
Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.
A. V. Marenich (2009)
Geometry optimization of molecules in solution: Joint use of the mean field approximation and the free-energy gradient method
I. F. Galván (2003)
Electron Transfer in Chemistry and Biology: An Introduction to the Theory
A. Kuznetsov (1999)
Charge generation in organic photovoltaics: a review of theory and computation
Kenley M Pelzer (2016)
Accurate and Efficient Treatment of Continuous Solute Charge Density in the Mean-Field QM/MM Free Energy Calculation.
H. Nakano (2013)
Controlling spin contamination using constrained density functional theory.
J. Schmidt (2008)
Efficient Computational Research Protocol to Survey Free Energy Surface for Solution Chemical Reaction in the QM/MM Framework: The FEG-ER Methodology and Its Application to Isomerization Reaction of Glycine in Aqueous Solution.
N. Takenaka (2016)
Simulation and modeling of the Rhodobacter sphaeroides bacterial reaction center II: Primary charge separation
M. Ceccarelli (2003)
Accurate magnetic exchange couplings in transition-metal complexes from constrained density-functional theory.
I. Rudra (2006)
Investigation of the free energy functions for electron transfer reactions
G. King (1990)
Electronic-Structure Theory of Organic Semiconductors: Charge-Transport Parameters and Metal/Organic Interfaces
V. Coropceanu (2013)
Dynamic nature of the intramolecular electronic coupling mediated by a solvent molecule: a computational study.
A. Troisi (2004)
Effect of solvent polarization on the reorganization energy of electron transfer from molecular dynamics simulations.
E. Vladimirov (2008)
Multistate Density Functional Theory for Effective Diabatic Electronic Coupling.
H. Ren (2016)
Direct optimization method to study constrained systems within density-functional theory
Qin Wu (2005)
Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces
A. M. Souza (2013)
Theoretical study of temperature and solvent dependence of the free-energy surface of the intramolecular electron-transfer based on the RISM-SCF theory: application to the 1,3-dinitrobenzene radical anion in acetonitrile and methanol.
Norio Yoshida (2008)
Constrained subsystem density functional theory.
P. Ramos (2016)
Role of protein frame and solvent for the redox properties of azurin from Pseudomonas aeruginosa
M. Cascella (2006)
Fourier analysis, correlation functions and nonadiabatic electron transfer: Wavepackets and exact representations
A. D. Hammerich (1994)
Electron transfer within a reaction path model calibrated by constrained DFT calculations: application to mixed-valence organic compounds.
E. Mangaud (2015)
Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level.
N. Gillet (2016)
Optimal diabatic bases via thermodynamic bounds.
S. Yeganeh (2011)
Constrained Density Functional Theory and Its Application in Long-Range Electron Transfer.
Qin Wu and (2006)
Linking the historical and chemical definitions of diabatic states for charge and excitation energy transfer reactions in condensed phase.
M. Pavanello (2011)
MCSCF study of the avoided curve crossing of the two lowest 1Σ+ states of LiF
H. Werner (1981)
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T. Yamaguchi (2020)
A polarizable molecular dynamics method for electrode-electrolyte interfacial electron transfer under the constant chemical-potential-difference condition on the electrode electrons.
K. Takahashi (2020)
Wannier-function-based constrained DFT with nonorthogonality-correcting Pulay forces in application to the reorganization effects in graphene-adsorbed pentacene
Subhayan Roychoudhury (2018)
A solvent-solute cooperative mechanism for symmetry-breaking charge transfer.
Changmin Lee (2020)