Time-dependent density functional approach for the calculation of inelastic x-ray scattering spectra of molecules.

We apply time-dependent density functional theory to study the valence electron excitations of molecules and generalize the typically used time-propagation scheme and Casida's method to calculate the full wavevector dependent response function. This allows the computational study of dipole-forbidden valence electron transitions and the dispersion of spectral weight as a function of the wavevector. The method provides a novel analysis tool for spectroscopic methods such as inelastic x-ray scattering and electron energy loss spectroscopy. We present results for benzene and CF(3)Cl and make a comparison with experimental results.

[1]  Kieron Burke,et al.  Time-dependent density functional theory: past, present, and future. , 2005, The Journal of chemical physics.

[2]  P. C. Gibbons,et al.  Electronic Excitations in LiF: 10-70 eV , 1977 .

[3]  A. Shukla,et al.  Momentum Dependence of Fluorine K-Edge Core Exciton in LiF , 2002 .

[4]  E. Gross,et al.  Density-Functional Theory for Time-Dependent Systems , 1984 .

[5]  X. Andrade,et al.  Efficient formalism for large-scale ab initio molecular dynamics based on time-dependent density functional theory. , 2007, Physical review letters.

[6]  J. Rehr,et al.  Experimental determination of the core-excited electron density of states , 2006 .

[7]  K. Leung.  VALENCE AND INNER SHELL NON-DIPOLE EXCITATION SPECTROSCOPY OF POLYATOMIC MOLECULES BY ANGLE-RESOLVED INELASTIC ELECTRON SCATTERING AT HIGH ENERGY , 1999 .

[8]  M. Rocco,et al.  Absolute differential cross sections for elastic and inelastic electron scattering from benzene with 1 kev impact energy , 2000 .

[9]  E. Gross,et al.  Time-dependent density functional theory. , 2004, Annual review of physical chemistry.

[10]  A. Zunger,et al.  Self-interaction correction to density-functional approximations for many-electron systems , 1981 .

[11]  L. Reining,et al.  Double excitations in finite systems. , 2009, The Journal of chemical physics.

[12]  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.

[13]  Manfred Lein,et al.  Numerical aspects of real-space approaches to strong-field electron dynamics , 2007, J. Comput. Phys..

[14]  P. Midgley,et al.  Electron tomography and holography in materials science. , 2009, Nature materials.

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

[16]  Kendall Atkinson,et al.  Numerical integration on the sphere , 1982, The Journal of the Australian Mathematical Society. Series B. Applied Mathematics.

[17]  R. V. Van Duyne,et al.  Molecular Plasmonics , 2004, Science.

[18]  Rez,et al.  Dipole-forbidden excitations in electron-energy-loss spectroscopy. , 1989, Physical review. B, Condensed matter.

[19]  Bertsch,et al.  Time-dependent local-density approximation in real time. , 1996, Physical review. B, Condensed matter.

[20]  U. Bergmann,et al.  Bulk-sensitive XAS characterization of light elements: from X-ray Raman scattering to X-ray Raman spectroscopy , 2002 .

[21]  D. Muller,et al.  Three-dimensional imaging of nonspherical silicon nanoparticles embedded in silicon oxide by plasmon tomography , 2006 .

[22]  D. Pines,et al.  The theory of quantum liquids , 1968 .

[23]  K. Yabana,et al.  Photoabsorption spectra in the continuum of molecules and atomic clusters , 2000, physics/0010025.

[24]  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 .

[25]  K. Hämäläinen,et al.  Inelastic x-ray scattering study of collective electron excitations in MgB2 , 2005 .

[26]  A. Sakko,et al.  Density functional study of x-ray Raman scattering from aromatic hydrocarbons and polyfluorene , 2007 .

[27]  Quong,et al.  First-principles evaluation of dynamical response and plasmon dispersion in metals. , 1993, Physical review letters.

[28]  L. Tjeng,et al.  Nonresonant inelastic x-ray scattering involving excitonic excitations: the examples of NiO and CoO. , 2007, Physical review letters.

[29]  George F. Bertsch,et al.  Time-dependent local-density approximation in real time , 1996 .

[30]  P. Jørgensen.  Molecular and Atomic Applications of Time-Dependent Hartree-Fock Theory , 1975 .

[31]  Kieron Burke,et al.  Basics of TDDFT , 2006 .

[32]  E. Burkel.  Determination of phonon dispersion curves by means of inelastic x-ray scattering , 2001 .

[33]  L. Reining,et al.  Signatures of short-range many-body effects in the dielectric function of silicon for finite momentum transfer. , 2006, Physical review letters.

[34]  Mikael P. Johansson,et al.  Coupled-cluster and density functional theory studies of the electronic excitation spectra of trans-1,3-butadiene and trans-2-propeniminium. , 2009, The Journal of chemical physics.

[35]  Dietrich Foerster,et al.  On the Kohn-Sham density response in a localized basis set. , 2009, The Journal of chemical physics.

[36]  Angel Rubio,et al.  TDDFT from Molecules to Solids: The Role of Long-Range Interactions , 2005 .

[37]  G. Seidler,et al.  A pressure cell for nonresonant inelastic x-ray scattering studies of gas phases. , 2008, The Review of scientific instruments.

[38]  Jacek A. Majewski,et al.  Exact Kohn-Sham Exchange Potential in Semiconductors , 1997 .

[39]  Ivano Tavernelli,et al.  Electronic density response of liquid water using time-dependent density functional theory , 2006 .

[40]  F. Sette,et al.  MOMENTUM TRANSFER DEPENDENCE OF INELASTIC X-RAY SCATTERING FROM THE LI K EDGE , 1997 .

[41]  C. Winstead,et al.  Observation of a “new” quadrupole transition at 7.7 eV in CF3Cl by momentum-transfer-resolved electron energy loss spectroscopy , 1993 .

[42]  G. Vankó,et al.  Multiple-element spectrometer for non-resonant inelastic X-ray spectroscopy of electronic excitations. , 2009, Journal of synchrotron radiation.

[43]  Peter Abbamonte,et al.  Dynamical reconstruction of the exciton in LiF with inelastic x-ray scattering , 2008, Proceedings of the National Academy of Sciences.

[44]  Andreas Görling,et al.  Charge-transfer excitation energies with a time-dependent density-functional method suitable for orbital-dependent exchange-correlation kernels , 2009 .

[45]  Excitonic optical spectrum of semiconductors obtained by time-dependent density-functional theory with the exact-exchange kernel. , 2002, Physical review letters.

[46]  Pina Romaniello,et al.  Time-dependent current-density-functional theory for the metallic response of solids , 2005 .

[47]  Winfried Schulke,et al.  Electron dynamics by inelastic X-ray scattering , 2007 .

[48]  Imaging density disturbances in water with a 41.3-attosecond time resolution. , 2003, Physical review letters.