Coupled quantum-classical method for long range charge transfer: relevance of the nuclear motion to the quantum electron dynamics

Charge and excitonic-energy transfer phenomena are fundamental for energy conversion in solar cells as well as artificial photosynthesis. Currently, much interest is being paid to light-harvesting and energy transduction processes in supramolecular structures, where nuclear dynamics has a major influence on electronic quantum dynamics. For this reason, the simulation of long range electron transfer in supramolecular structures, under environmental conditions described within an atomistic framework, has been a difficult problem to study. This work describes a coupled quantum mechanics/molecular mechanics method that aims at describing long range charge transfer processes in supramolecular systems, taking into account the atomistic details of large molecular structures, the underlying nuclear motion, and environmental effects. The method is applied to investigate the relevance of electron–nuclei interaction on the mechanisms for photo-induced electron–hole pair separation in dye-sensitized interfaces as well as electronic dynamics in molecular structures.

[1]  Jan‐Ole Joswig,et al.  Intramolecular Polarization Induces Electron–Hole Charge Separation in Light-Harvesting Molecular Triads , 2014 .

[2]  A. Akimov,et al.  Persistent Electronic Coherence Despite Rapid Loss of Electron Nuclear Correlation , 2013 .

[3]  L. Rego,et al.  Chapter 4:Modelling electron quantum dynamics in large molecular systems , 2013 .

[4]  Jameel A. Hasan,et al.  Ultrafast Interfacial Charge-Transfer Dynamics in a Donor-π-Acceptor Chromophore Sensitized TiO2 Nanocomposite , 2013 .

[5]  L. Rego,et al.  Coupled Electron–Hole Quantum Dynamics on D−π–A Dye-Sensitized TiO2 Semiconductors , 2012 .

[6]  M. Oviedo,et al.  Quantum Dynamical Simulations as a Tool for Predicting Photoinjection Mechanisms in Dye-Sensitized TiO2 Solar Cells. , 2012, The journal of physical chemistry letters.

[7]  F. Willig,et al.  Ultrafast photoinduced electron transfer at electrodes: the general case of a heterogeneous electron-transfer reaction. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[8]  M. Oviedo,et al.  Quantum Dynamics of Light-Induced Charge Injection in a Model Dye–Nanoparticle Complex , 2012 .

[9]  F. Willig,et al.  Dynamics of ultrafast photoinduced heterogeneous electron transfer, implications for recent solar energy conversion scenarios , 2012 .

[10]  Basile F. E. Curchod,et al.  Nonadiabatic molecular dynamics with solvent effects: A LR-TDDFT QM/MM study of ruthenium (II) tris (bipyridine) in water , 2011 .

[11]  Graham R Fleming,et al.  Lessons from nature about solar light harvesting. , 2011, Nature chemistry.

[12]  L. Rego,et al.  Subpicosecond Dynamics of Metal-to-Ligand Charge-Transfer Excited States in Solvated [Ru(bpy)3]2+ Complexes , 2011 .

[13]  K. Schulten,et al.  From atomistic modeling to excitation transfer and two-dimensional spectra of the FMO light-harvesting complex. , 2011, The journal of physical chemistry. B.

[14]  K. Schulten,et al.  Theory and Simulation of the Environmental Effects on FMO Electronic Transitions. , 2011, The journal of physical chemistry letters.

[15]  V. May,et al.  Charge and Energy Transfer Dynamics in Molecular Systems: MAY:CHARGE TRANSFER 3ED O-BK , 2011 .

[16]  Gonghu Li,et al.  Energy conversion in natural and artificial photosynthesis. , 2010, Chemistry & biology.

[17]  I. Tavernelli,et al.  Electron localization dynamics in the triplet excited state of [Ru(bpy)3]2+ in aqueous solution. , 2010, Chemistry.

[18]  David N. Beratan,et al.  Fluctuations in biological and bioinspired electron-transfer reactions. , 2010, Annual review of physical chemistry.

[19]  Tracey M. Clarke,et al.  Charge photogeneration in organic solar cells. , 2010, Chemical reviews.

[20]  T. Moore,et al.  Solar fuels via artificial photosynthesis. , 2009, Accounts of chemical research.

[21]  Bradley F. Habenicht,et al.  Phonon-induced dephasing of excitons in semiconductor quantum dots: multiple exciton generation, fission, and luminescence. , 2009, ACS nano.

[22]  David Beljonne,et al.  Beyond Förster resonance energy transfer in biological and nanoscale systems. , 2009, The journal of physical chemistry. B.

[23]  Walter R. Duncan,et al.  Photoinduced electron dynamics at the chromophore-semiconductor interface: A time-domain ab initio perspective , 2009 .

[24]  J. D. Gezelter,et al.  Is the Ewald summation still necessary? Pairwise alternatives to the accepted standard for long-range electrostatics. , 2006, The Journal of chemical physics.

[25]  A. Nitzan.  Chemical Dynamics in Condensed Phases: Relaxation, Transfer, and Reactions in Condensed Molecular Systems , 2006 .

[26]  V. Batista,et al.  Influence of thermal fluctuations on interfacial electron transfer in functionalized TiO2 semiconductors. , 2005, Journal of the American Chemical Society.

[27]  J. Davidsson,et al.  Femtosecond transient absorption anisotropy study on [Ru(bpy)3]2+ and [Ru(bpy)(py)4]2+. Ultrafast interligand randomization of the MLCT state. , 2005, The journal of physical chemistry. A.

[28]  Brian A. Gregg,et al.  Excitonic Solar Cells , 2003 .

[29]  S. Skourtis.  Electron transfer through time-dependent bridges: tunneling by virtual transitions that break the Born–Oppenheimer approximation , 2003 .

[30]  Stefan M. Kast,et al.  Enhancement of the wolf damped Coulomb potential: Static, dynamic, and dielectric properties of liquid water from molecular simulation , 2002 .

[31]  R. Friesner,et al.  Evaluation and Reparametrization of the OPLS-AA Force Field for Proteins via Comparison with Accurate Quantum Chemical Calculations on Peptides† , 2001 .

[32]  T. Moore,et al.  Mimicking photosynthetic solar energy transduction. , 2001, Accounts of chemical research.

[33]  Volkhard May,et al.  Charge and Energy Transfer Dynamics in Molecular Systems: A Theoretical Introduction , 2000 .

[34]  S. Phillpot,et al.  Exact method for the simulation of Coulombic systems by spherically truncated, pairwise r−1 summation , 1999 .

[35]  Sándor Suhai,et al.  Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties , 1998 .

[36]  G. Cerullo,et al.  Femtosecond Dynamics of Excited-State Evolution in [Ru(bpy)3]2+ , 1997, Science.

[37]  W. L. Jorgensen,et al.  Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids , 1996 .

[38]  G. Seifert,et al.  Calculations of molecules, clusters, and solids with a simplified LCAO-DFT-LDA scheme , 1996 .

[39]  Seifert,et al.  Construction of tight-binding-like potentials on the basis of density-functional theory: Application to carbon. , 1995, Physical review. B, Condensed matter.

[40]  P. Kollman,et al.  A Second Generation Force Field for the Simulation of Proteins, Nucleic Acids, and Organic Molecules , 1995 .

[41]  M. Field.  A molecular dynamics simulation of photo-induced electron transfer in an organic donor—acceptor compound , 1992 .