Classical Electrodynamics Coupled to Quantum Mechanics for Calculation of Molecular Optical Properties: a RT-TDDFT/FDTD Approach

A new multiscale computational methodology was developed to effectively incorporate the scattered electric field of a plasmonic nanoparticle into a quantum mechanical (QM) optical property calculation for a nearby dye molecule. For a given location of the dye molecule with respect to the nanoparticle, a frequency-dependent scattering response function was first determined by the classical electrodynamics (ED) finite-difference time-domain (FDTD) approach. Subsequently, the time-dependent scattered electric field at the dye molecule was calculated using the FDTD scattering response function through a multidimensional Fourier transform to reflect the effect of polarization of the nanoparticle on the local field at the molecule. Finally, a real-time time-dependent density function theory (RT-TDDFT) approach was employed to obtain a desired optical property (such as absorption cross section) of the dye molecule in the presence of the nanoparticle’s scattered electric field. Our hybrid QM/ED methodology was de...

[1]  G. Schatz,et al.  On the linear response and scattering of an interacting molecule-metal system. , 2009, The Journal of chemical physics.

[2]  J. Creighton.  Contributions to the early development of surface-enhanced Raman spectroscopy , 2010, Notes and Records of the Royal Society.

[3]  J. F. Stoddart,et al.  Photoconductance and inverse photoconductance in films of functionalized metal nanoparticles , 2009, Nature.

[4]  J. Hupp,et al.  Distance dependence of plasmon-enhanced photocurrent in dye-sensitized solar cells. , 2009, Journal of the American Chemical Society.

[5]  Daniel Neuhauser,et al.  Multiscale Maxwell-Schrodinger modeling: A split field finite-difference time-domain approach to molecular nanopolaritonics. , 2009, The Journal of chemical physics.

[6]  Lasse Jensen,et al.  Understanding the molecule-surface chemical coupling in SERS. , 2009, Journal of the American Chemical Society.

[7]  George C. Schatz,et al.  Correlating the Structure, Optical Spectra, and Electrodynamics of Single Silver Nanocubes , 2009 .

[8]  M. Ratner,et al.  Raman scattering from nonequilibrium molecular conduction junctions. , 2009, Nano letters.

[9]  Logan K. Ausman,et al.  Methods for describing the electromagnetic properties of silver and gold nanoparticles. , 2008, Accounts of chemical research.

[10]  George C Schatz,et al.  Electronic structure methods for studying surface-enhanced Raman scattering. , 2008, Chemical Society reviews.

[11]  Michael Galperin,et al.  Linear optical response of current-carrying molecular junction: a nonequilibrium Green's function-time-dependent density functional theory approach. , 2008, The Journal of chemical physics.

[12]  John R. Lombardi,et al.  A Unified Approach to Surface-Enhanced Raman Spectroscopy , 2008 .

[13]  J J Rehr,et al.  Real-time time-dependent density functional theory approach for frequency-dependent nonlinear optical response in photonic molecules. , 2007, The Journal of chemical physics.

[14]  Walter R. Duncan,et al.  Theoretical studies of photoinduced electron transfer in dye-sensitized TiO2. , 2007, Annual review of physical chemistry.

[15]  J. Cuevas,et al.  Photoconductance of organic single-molecule contacts , 2007, 0704.0408.

[16]  H. Appel,et al.  octopus: a tool for the application of time‐dependent density functional theory , 2006 .

[17]  Stefan Goedecker,et al.  Efficient solution of Poisson's equation with free boundary conditions. , 2006, The Journal of chemical physics.

[18]  Abraham Nitzan,et al.  Optical properties of current carrying molecular wires. , 2006, The Journal of chemical physics.

[19]  Matthias Krack,et al.  Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals , 2005 .

[20]  Michele Parrinello,et al.  Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach , 2005, Comput. Phys. Commun..

[21]  Current-induced light emission and light-induced current in molecular-tunneling junctions. , 2005, Physical review letters.

[22]  Angel Rubio,et al.  Propagators for the time-dependent Kohn-Sham equations. , 2004, The Journal of chemical physics.

[23]  Evert Jan Baerends,et al.  Asymptotic correction of the exchange-correlation kernel of time-dependent density functional theory for long-range charge-transfer excitations. , 2004, The Journal of chemical physics.

[24]  S. J. van der Molen,et al.  One-way optoelectronic switching of photochromic molecules on gold. , 2003, Physical review letters.

[25]  M. Grätzel.  Dye-sensitized solar cells , 2003 .

[26]  E. Coronado,et al.  The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment , 2003 .

[27]  Markus Reiher,et al.  Quantum chemical calculation of vibrational spectra of large molecules—Raman and IR spectra for Buckminsterfullerene , 2002, J. Comput. Chem..

[28]  Stefan Grafström,et al.  Photoassisted scanning tunneling microscopy , 2002 .

[29]  Jacopo Tomasi,et al.  Enhanced response properties of a chromophore physisorbed on a metal particle , 2001 .

[30]  E. J. Baerends,et al.  Approximation of the exchange-correlation Kohn-Sham potential with a statistical average of different orbital model potentials. , 1999 .

[31]  Dennis R. Salahub,et al.  Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold , 1998 .

[32]  T. Yoko,et al.  Effects of the incorporation of silver and gold nanoparticles on the photoanodic properties of rose bengal sensitized TiO2 film electrodes prepared by sol-gel method , 1997 .

[33]  Steven R. Emory,et al.  Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering , 1997, Science.

[34]  G. Pelosi,et al.  Finite-element methods in microwaves: a selected bibliography , 1996 .

[35]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[36]  Anne B. Myers,et al.  Solvent Effects in the Raman Spectra of the Triiodide Ion: Observation of Dynamic Symmetry Breaking and Solvent Degrees of Freedom , 1996 .

[37]  David E. Woon,et al.  Gaussian basis sets for use in correlated molecular calculations. IV. Calculation of static electrical response properties , 1994 .

[38]  Mohammad Khaja Nazeeruddin,et al.  Conversion of light to electricity by cis-X2bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) charge-transfer sensitizers (X = Cl-, Br-, I-, CN-, and SCN-) on nanocrystalline titanium dioxide electrodes , 1993 .

[39]  D. F. Eaton,et al.  Nonlinear Optical Materials , 1991, Science.

[40]  Cynthia Furse,et al.  Improvements to the finite-difference time-domain method for calculating the radar cross section of a perfectly conducting target , 1990 .

[41]  Frederick W. King,et al.  Theory of Raman scattering by molecules adsorbed on electrode surfaces , 1978 .

[42]  D. L. Jeanmaire,et al.  Surface raman spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode , 1977 .

[43]  R. W. Christy,et al.  Optical Constants of the Noble Metals , 1972 .

[44]  J. Crank,et al.  A practical method for numerical evaluation of solutions of partial differential equations of the heat-conduction type , 1947, Mathematical Proceedings of the Cambridge Philosophical Society.

[45]  K. S. Krishnan,et al.  A New Type of Secondary Radiation , 1928, Nature.

[46]  E. Schrödinger.  An Undulatory Theory of the Mechanics of Atoms and Molecules , 1926 .

[47]  James Clerk Maxwell,et al.  VIII. A dynamical theory of the electromagnetic field , 1865, Philosophical Transactions of the Royal Society of London.