Soft-X-Ray Photoabsorption of the No Dimer

X-ray absorption spectra are reported for the first time for the (NO)2 dimer at both the nitrogen and oxygen K edges, the data being obtained from (NO)2 multilayers formed on Ag{111}. The spectra display distinctive features which suggest an electronic structure for excited states of this species. Density functional theory studies of the core-hole excited states provide the basis for spectral assignments at the nitrogen K edge, allowing the identification of the N 1s electron promotion into the 2b1, 2a2, 7b2, 8a1 and 8b2 orbitals. Correlations are found between the experimental integrated oscillator strengths of the two π* states, at the nitrogen K edge, and the N-localized 2p coefficients of the unoccupied orbitals of the (1A1) state.

[1]  P. Decleva,et al.  Density functional calculations of excitation energies and oscillator strengths for and excitations and ionization potentials in carbonyl containing molecules , 1995 .

[2]  B. Roos,et al.  A theoretical determination of the dissociation energy of the nitric oxide dimer , 1994 .

[3]  B. Dunlap,et al.  The σ* absorption peak at the oxygen 1s edge of O2: Exchange splitting, ultrafast dissociation, and atomiclike Auger spectra , 1994 .

[4]  D. Salahub,et al.  Density functional study of nitrogen oxides , 1994 .

[5]  C. W. Murray,et al.  Quadrature schemes for integrals of density functional theory , 1993 .

[6]  D. A. King,et al.  A high‐energy spherical grating monochromator for soft x rays at the Daresbury SRS , 1992 .

[7]  K. Honma,et al.  Photodissociation of the NO dimer: rotational energy distribution and alignment of the NO(B 2Π) fragments , 1992 .

[8]  S. Aminpirooz,et al.  HIGH RESOLUTION NEXAFS STUDIES OF AROMATIC MOLECULES ADSORBED AND CONDENSED ON NI(111) , 1991 .

[9]  R. D. Harcourt.  The origin of the long N-N bond in N2O2: an ab initio valence bond study , 1990 .

[10]  Somers,et al.  Application of molecular symmetry in near-edge x-ray-absorption spectroscopy of adsorbed species. , 1989, Physical review. B, Condensed matter.

[11]  H. Schaefer,et al.  Theoretical investigations of molecules composed only of fluorine, oxygen and nitrogen: determination of the equilibrium structures of FOOF, (NO)2 and FNNF and the transition state structure for FNNF cis-trans isomerization , 1989 .

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

[13]  J. Montgomery,et al.  The electronic structure and stability of asymmetric dinitrogen dioxide (a‐N2O2) , 1988 .

[14]  I. V. Kondratieva,et al.  Theoretical treatment of X-ray absorption fine structure by the localized orbitals method , 1988 .

[15]  Ishii,et al.  Absolute oscillator strengths from K-shell electron-energy-loss spectra of the fluoroethenes and 1,3-perfluorobutadiene. , 1987, Physical review. A, General physics.

[16]  A. Hitchcock,et al.  A quantitative experimental study of the core excited electronic states of formamide, formic acid, and formyl fluoride , 1987 .

[17]  J. Perdew,et al.  Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation. , 1986, Physical review. B, Condensed matter.

[18]  R. G. Rothwell,et al.  Photoelectron spectroscopy of the NO dimer , 1986 .

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

[20]  K. Honma,et al.  Formation of electronically excited nitric oxide and energy partitioning in the 193-nm photolysis of the nitric oxide dimer , 1985 .

[21]  C. R. Brundle,et al.  Summary Abstract: Decomposition of NO on Ag(111) at low temperatures , 1984 .

[22]  C. R. Brundle,et al.  Core level photoemission of the no dimer: Theory and Experimental realization for NO/Ag(111) , 1984 .

[23]  R. P. Messmer,et al.  Many‐electron effects in the photoelectron spectra of condensed nitric oxide , 1984 .

[24]  W. R. Salaneck,et al.  Intermolecular Screening in Core-Level Photoemission from the Nitric-Oxide Dimer , 1983 .

[25]  C. Bock,et al.  Intramolecular interaction effects and the structure of N2OS and N2O2: An Ab initio study , 1983 .

[26]  J. P. Ritchie.  Comments on the cis, trans, and cyclic dimers of nitric oxide , 1983 .

[27]  S. Kukolich.  Structure and quadrupole coupling measurements on the NO dimer , 1983 .

[28]  R. Bardo.  A theoretical prediction of the structure and energy of the metastable symmetric cis-nitric oxide dimer , 1982 .

[29]  Stewart E. Novick,et al.  Molecular beam electric resonance spectroscopy of the nitric oxide dimer , 1981 .

[30]  T. Ha.  Ab initio CI study of the nitric oxide dimer (N2O2) , 1981 .

[31]  M. Vincent,et al.  A molecular orbital comparison of the asymmetric and symmetric nitric oxide dimers , 1981 .

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

[33]  J. Coulomb,et al.  Two-Dimensional First-Order Melting Transition and Polymorphism in a Monolayer of Nitric Oxide Adsorbed on Graphite , 1978 .

[34]  G. Ewing,et al.  Van Der Waals Molecules , 1976 .

[35]  J. E. Boggs,et al.  Structure and force fields of the isomers of dinitrogen dioxide , 1976 .

[36]  W. Schwarz.  X-Ray Absorption Spectroscopy on Free Molecules , 1974 .

[37]  T. Vladimiroff.  Ab initio molecular orbital studies of cyclic nitric oxide dimer , 1972 .

[38]  G. Ewing.  Intermolecular Interactions: van der Waals Molecules , 1972 .

[39]  J. Murrell,et al.  Structure and stability of the nitric oxide dimer , 1971 .

[40]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[41]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[42]  H. L. Johnston,et al.  The Magnetic Susceptibility of Liquid Nitric Oxide and the Heat of Dissociation of (NO)21 , 1952 .

[43]  Allen L. Johnson,et al.  Inner-shell spectroscopies of solid and gaseous alkylidyne tricobalt nonacarbonyl complexes , 1993 .

[44]  V. Akimov,et al.  Quasiatomic treatment of near-edge-structure features in X-ray absorption spectra of first-row polyatomic systems , 1990 .

[45]  Alistair P. Rendell,et al.  Comparison of the quadratic configuration interaction and coupled cluster approaches to electron correlation including the effect of triple excitations , 1990 .

[46]  J. Mason.  The dimeric nitrogen oxides. Part I. Electronic absorption of the nitrogen oxide dimer, and comparison of observed and calculated spectra for dinitrogen dioxide, trioxide, and tetraoxide , 1975 .

[47]  A. B. Callear,et al.  Investigation of the 2050 Å system of the nitric oxide dimer , 1971 .

[48]  F. Cotton.  Chemical Applications of Group Theory , 1971 .

[49]  B. M. Gimarc.  Shapes of simple polyatomic molecules and ions. I. Series HAAH and BAAB , 1970 .

[50]  Janine Mayence.  Spectres d'absorption à basse température. Étude de N2O gazeux et de NO gazeux et liquide , 1952 .

[51]  H. Bernstein,et al.  Ultraviolet Absorption Spectrum of Nitric Oxide , 1947 .

[52]  L. Pauling.  The Nature Of The Chemical Bond , 1939 .