Time-Dependent Density Functional Theory Study of the X-ray Absorption Spectroscopy of Acetylene, Ethylene, and Benzene on Si(100)

The carbon 1s X-ray absorption spectroscopy (XAS) of acetylene, ethylene, and benzene in gas phase and adsorbed on the Si(100) surface is studied using time-dependent density functional theory (TDDFT) with hybrid exchange correlation functionals. The computed spectra are sensitive to the proportion of Hartree−Fock exchange in the exchange-correlation functional. The fraction of Hartree−Fock exchange is optimized to provide accurate predictions of the 1s → π* excitation energies. In gas phase, the spectra of acetylene, ethylene and benzene are dominated by 1s → π* excitations with further weaker bands at higher energies below the ionization threshold arising predominantly from Rydberg excitations. In the spectrum for ethane, bands arising from excitation to Rydberg and excitations are observed. For the molecules adsorbed on Si(100), excitations to Rydberg states are less evident. The calculations indicate that acetylene adsorbed on the Si(100) surface has an intense π* band, which lies 1.5 eV lower than in...

[1]  Allen L. Johnson,et al.  Near-edge X-ray-absorption fine-structure studies of chemisorbed hydrocarbons: bond lengths with a ruler , 1984 .

[2]  C. Theodosiou Evaluation of penetration effects in high-l Rydberg states , 1983 .

[3]  Adam P. Hitchcock,et al.  Resonances in the K shell excitation spectra of benzene and pyridine: Gas phase, solid, and chemisorbed states , 1985 .

[4]  Anders Nilsson,et al.  X-ray absorption spectra of water within a plane-wave Car-Parrinello molecular dynamics framework. , 2004, The Journal of chemical physics.

[5]  Ross D. Adamson,et al.  Empirical density functionals , 1998 .

[6]  H. Ågren,et al.  Benzene adsorbed on Cu(110): theoretical X-ray absorption, emission and shake calculations , 1998 .

[7]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[8]  N. Kosugi,et al.  C 1s -->pi* excitation in variable size benzene clusters. , 2006, Physical chemistry chemical physics : PCCP.

[9]  A. Hitchcock,et al.  Fluorination effects on the inner-shell spectra of unsaturated molecules , 1988 .

[10]  M. Nagasono,et al.  Polarization and angle-resolved NEXAFS of benzene adsorbed on oriented single-domain Si(001)-2×1 surfaces , 2003 .

[11]  Acetylene on Si(100) from first principles: adsorption geometries, equilibrium coverages, and thermal decomposition , 2000, cond-mat/0011084.

[12]  P. W. Langhoff,et al.  Theoretical studies of photoionization in C2H2, C2H4, and C2H6: correlation of prominent spectra features with CC and CH antibonding orbitals , 1991 .

[13]  U. Hergenhahn,et al.  Reappraisal of the Existence of Shape Resonances in the Series C{sub 2}H{sub 2} , C{sub 2}H{sub 4} , and C{sub 2}H{sub 6} , 1997 .

[14]  M. Causà,et al.  X-ray absorption spectroscopy of titanium oxide by time dependent density functional calculations. , 2006, The journal of physical chemistry. B.

[15]  J. Yoshinobu,et al.  The adsorption and thermal decomposition of acetylene on Si(100) and vicinal Si(100)9 , 1987 .

[16]  W. H. Weinberg,et al.  Adsorption of acetylene on the Si(100)‐(2×1) surface , 1993 .

[17]  H. Nakai,et al.  Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: core-valence-Rydberg B3LYP. , 2006, The Journal of chemical physics.

[18]  A. Becke A New Mixing of Hartree-Fock and Local Density-Functional Theories , 1993 .

[19]  L. Pettersson,et al.  MO and DFT approaches to the calculation of X-ray absorption/emission spectra of nitrogen atom adsorbed on Cu(100) , 1998 .

[20]  I. Affleck,et al.  Soliton approach to spin-Peierls antiferromagnets: Large-scale numerical results , 1998, cond-mat/9805386.

[21]  N. Besley Calculation of the electronic spectra of molecules in solution and on surfaces , 2004 .

[22]  Mauro Stener,et al.  Time dependent density functional theory of core electrons excitations , 2003 .

[23]  Benjamin T. Miller,et al.  A parallel implementation of the analytic nuclear gradient for time-dependent density functional theory within the Tamm–Dancoff approximation , 1999 .

[24]  R. Bartlett,et al.  Description of core‐excitation spectra by the open‐shell electron‐attachment equation‐of‐motion coupled cluster method , 1995 .

[25]  D. P. Woodruff,et al.  Local adsorption geometry of acetylene on Si(100)(2×1) , 2000 .

[26]  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 .

[27]  D. Nordlund,et al.  Geometric structure and chemical bonding of acetylene adsorbed on Cu(1 1 0) , 2004 .

[28]  W. Butscher,et al.  Theoretical study of the core-ionized and various core-excited and shake-up states of acetylene and ethylene by ab initio MRD-CI methods , 1980 .

[29]  N. Besley Theoretical study of the electronic spectroscopy of CO adsorbed on Pt(111). , 2005, The Journal of chemical physics.

[30]  H. Nakai,et al.  Time-dependent density functional theory calculations for core-excited states: assessment of standard exchange-correlation functionals and development of a novel hybrid functional. , 2006, The Journal of chemical physics.

[31]  M. Piancastelli The neverending story of shape resonances , 1999 .

[32]  Chen,et al.  Large On-Off Ratios and Negative Differential Resistance in a Molecular Electronic Device. , 1999, Science.

[33]  Meigs,et al.  Breaking of ground-state symmetry in core-excited ethylene and benzene. , 1989, Physical review letters.

[34]  A. Kilcoyne,et al.  A Comprehensive Photoabsorption, Photoionization, and Shake-up Excitation Study of the C 1s Cross Section of Benzene , 2000 .

[35]  Nicholas C. Handy,et al.  Improving virtual Kohn-Sham orbitals and eigenvalues: Application to excitation energies and static polarizabilities , 1998 .

[36]  gren,et al.  Calculation of near-edge x-ray-absorption spectra of molecules and polymers by a Green's-function method. , 1993, Physical review. B, Condensed matter.

[37]  P. W. Langhoff,et al.  Correlation of molecular valence‐ and K‐shell photoionization resonances with bond lengths , 1989 .

[38]  A. Becke Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[39]  M. Frisch,et al.  Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields , 1994 .

[40]  J. Feldhaus,et al.  One-electron versus multielectron effects in the near-threshold C 1s photoionization of acetylene , 1997 .

[41]  Julia G. Lyubovitsky,et al.  NEXAFS studies of adsorption of benzene on Si(100)-2×1 , 1998 .

[42]  Wende,et al.  Shape resonances of oriented molecules: ab initio theory and experiment on hydrocarbon molecules , 2000, Physical review letters.

[43]  J. Yoshinobu,et al.  The adsorbed states of ethylene on Si(100)c(4×2), Si(100)(2×1), and vicinal Si(100) 9°: Electron energy loss spectroscopy and low‐energy electron diffraction studies , 1987 .

[44]  S. Urquhart,et al.  Chemical Trends in the Near-Edge X-ray Absorption Fine Structure of Monosubstituted and Para-Bisubstituted Benzenes , 2004 .

[45]  C. E. Brion,et al.  Carbon K-shell excitation of C2H2, C2H4, C2H6 and C6H6 by 2.5 keV electron impact , 1977 .

[46]  A. Hitchcock,et al.  Studies of C 1s → π* triplet states of carbon monoxide, benzene, ethylene, and acetylene , 1994 .

[47]  D. Chong,et al.  Density functional computations for inner-shell excitation spectroscopy , 1996 .

[48]  M. Stener,et al.  Time dependent density functional theory of X-ray absorption spectroscopy of alkaline-earth oxides. , 2005, The journal of physical chemistry. B.

[49]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[50]  Andrew Zangwill,et al.  Density-functional approach to local-field effects in finite systems: Photoabsorption in the rare gases , 1980 .

[51]  T. C. Chang,et al.  CORE EXCITATIONS OF SYMMETRICAL AROMATIC MOLECULES. SPECIFIC CORRELATIONS IN THE VALENCE SHELL AND LOCALIZATION IN THE CORE SHELLS , 1987 .

[52]  P. Dirac Note on Exchange Phenomena in the Thomas Atom , 1930, Mathematical Proceedings of the Cambridge Philosophical Society.

[53]  H. Ågren,et al.  Core-hole effects in x-ray-absorption spectra of fullerenes , 1999 .

[54]  H. Ogasawara,et al.  XPS and XAS investigation of condensed and adsorbed n-octane on a Cu(110) surface , 2003 .

[55]  T. Yokoyama,et al.  X-ray absorption spectra of poly-p-phenylenes and polyacenes: localization of π orbitals , 1990 .

[56]  P. Decleva,et al.  Time-Dependent Density Functional Theory Calculations of Ligand K Edge and Metal L Edge X-ray Absorption of a Series of Oxomolybdenum Complexes , 2004 .

[57]  Anders Nilsson,et al.  Hydrogen bonding between adsorbed deprotonated glycine molecules on Cu(110) , 2003 .

[58]  R. Gillies,et al.  Rydberg-valence mixing in the carbon 1s near-edge X-ray absorption fine structure spectra of gaseous alkanes. , 2005, Journal of Physical Chemistry A.

[59]  Hans Ågren,et al.  Calculations of near-edge x-ray-absorption spectra of gas-phase and chemisorbed molecules by means of density-functional and transition-potential theory , 1998 .

[60]  H. Ågren,et al.  Near-edge core photoabsorption in polyacenes: model molecules for graphite , 1995 .

[61]  Anders Nilsson,et al.  Half or full core hole in density functional theory X-ray absorption spectrum calculations of water? , 2005, Physical chemistry chemical physics : PCCP.

[62]  C. Wöll,et al.  RYDBERG TRANSITIONS IN X-RAY ABSORPTION SPECTROSCOPY OF ALKANES : THE IMPORTANCE OF MATRIX EFFECTS , 1999 .

[63]  M. Nagasono,et al.  Adsorption geometry of C2H2 on the single-domain Si(001)-(2×1) surface: fully polarization resolved NEXAFS , 2004 .

[64]  Weitao Yang,et al.  First-principles study of the structural and electronic properties of ethylene adsorption on Si(100)-(2×1) surface , 1997 .

[65]  N. Kosugi,et al.  Experimental and theoretical studies of the (C 1s−1,π*)3Π state of CO: Momentum transfer dependence and vibrational structure , 1994 .

[66]  L. Pettersson,et al.  Ethylene on Cu(110) and Ni(110): electronic structure and bonding derived from X-ray spectroscopy and theory , 2004 .

[67]  Luis Serrano-Andrés,et al.  Does density functional theory contribute to the understanding of excited states of unsaturated organic compounds , 1999 .

[68]  M. Nagasono,et al.  Fully polarization resolved X-ray absorption spectroscopy of C2H4 on single-domain Si(001)-(2×1) , 2003 .

[69]  E. Umbach,et al.  Analysis of the x-ray absorption spectra of linear saturated hydrocarbons using the Xα scattered-wave method , 1998 .

[70]  T. Ohta,et al.  Adsorption and reaction of acetylene and ethylene on the Si(001)2×1 surface , 2000 .

[71]  A. Ankudinov,et al.  Shape resonances of oriented molecules , 2000 .

[72]  Jon Baker,et al.  Q‐Chem 2.0: a high‐performance ab initio electronic structure program package , 2000, J. Comput. Chem..

[73]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[74]  T. Ohta,et al.  Adsorption of acetylene and ethylene on the Si(001)2×1 surface studied by NEXAFS and UPS , 1998 .