Fine structure in the inner valence photoelectron spectra of N2 and CO

Liu, Z.F.; Bancroft, G.M.; Coatsworth, L. L.; Tan, K. H.

doi:10.1016/0009-2614(93)85578-c

Cited by 40 publications

(26 citation statements)

References 13 publications

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“…The synchrotron photoelectron spectra ͑PES͒ were obtained at the Canadian Synchrotron Radiation Facility ͑CSRF͒ at the Aladdin Storage Ring of the University of Wisconsin at Madison's Synchrotron Radiation Center ͑SRC͒. The spectra were collected using the McPherson photoelectron spectrometer equipped with a multichannel plate detector 48 in conjunction with both the grasshopper grazing incidence monochromator 49 with high and low energy gratings and the 3 m toroidal grating monochromator ͑3 m-TGM͒, 50 also with high and low energy gratings. Angular corrections are not required as the photoelectrons were collected at the pseudomagic angle.…”

Section: Methodsmentioning

confidence: 99%

“…The strong satellite at 27.4 eV, with an intensity of 39% of the 2a g primary peak in the Mg K␣ spectrum 32 was originally assigned as a 2 B 1u ͑considering the molecule to be in its proper yz orientation͒ correlation state. 12,31,32 The task of the earlier theoretical calculations [41][42][43][44][45][46][47][48][49][50][51] was to assign the five main bands ͑below 20 eV binding energy͒ through Koopmans' Theorem at the Hartree-Fock ͑HF͒ level. The first study that went beyond the HF approximation ͑Green's function method 35 ͒ was published in 1976.…”

Section: Introductionmentioning

confidence: 99%

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Correlation states of ethylene

Desjardins

Bawagan

Liu

et al. 1995

The Journal of Chemical Physics

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High resolution synchrotron photoelectron spectra ͑PES͒ of ethylene have been obtained at several photon energies in the range 30 to 220 eV. Further evidence is presented that the correlation ͑satellite͒ peak at 27.4 eV binding energy is ''intrinsic'' in nature. A new correlation peak at 21.4 eV binding energy, however, is found to be a ''dynamic'' correlation. Several PES of 1-13 C-ethylene have also been obtained and have been found to be identical to those of normal ethylene. Both of the correlation peaks are also present in the labeled species with similar photon energy behaviors. Sophisticated theoretical calculations are found to agree quantitatively with the experimental PES spectra.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Correlation states of ethylene

Desjardins

Bawagan

Liu

et al. 1995

The Journal of Chemical Physics

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“…We focus here on the highly excited states of the molecular nitrogen ion in the energy range of 22-34 eV relative to the ground state of the neutral molecule. This binding-energy range has been addressed extensively in the literature by electron spectroscopy [10,[16][17][18][19] and by ab initio methods [10,18,20,21]. Some electronic states (such as 2 2 AE þ u , 2 2 Å g , 2 2 Å u , and 3 2 AE þ g ) were well characterized using photoelectron spectroscopy, although this technique is not applicable to some other states in that energy range due to the low magnitude of the corresponding matrix elements.…”

Section: Introductionmentioning

confidence: 99%

Single-Molecule X-Ray Interferometry: Controlling Coupled Electron-Nuclear Quantum Dynamics and Imaging Molecular Potentials by Ultrahigh-Resolution Resonant Photoemission andAb InitioCalculations

et al. 2013

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This paper reports an advanced study of the excited ionic states of the gas-phase nitrogen molecule in the binding-energy region of 22-34 eV, combining ultrahigh-resolution resonant photoemission (RPE) and ab initio configuration-interaction calculations. The RPE spectra are recorded for nine photon energies within the N 1s ! Ã absorption resonance of N 2 by using a photon bandwidth that is considerably smaller than lifetime broadening, and the dependence on excitation energy of the decay spectra is analyzed and used for the first assignment of 12 highly overlapped molecular states. The effect on the RPE profile of avoided curve crossings between the final N þ 2 ionic states is discussed, based on theoretical simulations that account for vibronic coupling, and compared with the experimental data. By use of synchrotron radiation with high spectral brightness, it is possible to selectively promote the molecule to highly excited vibrational sublevels of a core-excited electronic state, thereby controlling the spatial distribution of the vibrational wave packets, and to accurately image the ionic molecular potentials. In addition, the mapping of the vibrational wave functions of the core-excited states using the bound final states with far-fromequilibrium bond lengths has been achieved experimentally for the first time. Theoretical analysis has revealed the rich femtosecond nuclear dynamics underlying the mapping phenomenon.

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“…Recently, fine analysis was performed for the vibrational structure of some satellites of CO and N 2 by high-resolution PES using synchrotron and He II radiations 13 and ultraviolet photoelectron spectroscopy (UPS) 14 . Liu et al 12 also observed the fine structure in inner-valence PES of CO and N 2 with a resolution better than 100 meV.…”

mentioning

confidence: 92%

“…Out of the extensive work on the satellite peaks, the valence ionization spectra of CO and N 2 molecules are of special interest, and have been studied in detail both experimentally [1][2][3][4][5][6][7][8][9][10][11][12][13][14] and theoretically [15][16][17][18][19][20][21][22][23][24][25] . These spectra show many satellite peaks with complex band structures due to strong electron correlations.…”

mentioning

confidence: 99%

Theoretical Fine Spectroscopy with SAC-CI Method: Outer- and Inner-Valence Ionization Spectra of CO and N2

Ehara

Ishida

Nakatsuji

2005

Collect. Czech. Chem. Commun.

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Dedicated to Professor Josef Paldus on the occasion of his 70th birthday.Outer-and inner-valence ionization spectra of CO and N 2 were studied by the SAC-CI (symmetry-adapted-cluster configuration-interaction) general-R method. Fine details of experimental spectra of these molecules were reproduced and quantitative assignments of the peaks were proposed. Both outer-and inner-valence satellites were classified into the shakeup states including the valence or Rydberg excitations. For CO, theoretical satellite spectrum up to 50 eV was presented and the nine bands of 22-50 eV observed by EMS and eight bands of 22-34 eV by XPS (C-K) were characterized in detail. Numerous satellite peaks with distributed intensity were obtained and some of them, especially for bands 4, 5, 6 and 7, were predominantly described by triple-electron processes. For N 2 , the spectrum up to 45 eV was calculated and the complex satellite peaks observed by XPS in the lower energy region 20-33 eV were interpreted. The detailed assignments for the (2σ g -1 ) satellite states in the higher-energy region 33-45 eV were also presented. Keywords: SAC-CI; Valence ionization spectra; Satellite spectra; Ab initio calculations; Photoelectron spectroscopy; Quantum chemistry.Many satellite peaks are usually involved in the inner-valence region of an ionization spectrum. They attracted considerable experimental and theoretical interests since they often provide information concerning electron correlations in molecules. Recently, extensive experimental studies of these peaks have been performed by high-resolution synchrotron radiation photoelectron spectroscopy (SRPES), X-ray photoelectron spectroscopy (XPS), and electron momentum spectroscopy (EMS). In parallel, advanced theoretical methods have also been used for detailed and quantitative assignments of these peaks.

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Fine structure in the inner valence photoelectron spectra of N2 and CO

Cited by 40 publications

References 13 publications

Correlation states of ethylene

Correlation states of ethylene

Single-Molecule X-Ray Interferometry: Controlling Coupled Electron-Nuclear Quantum Dynamics and Imaging Molecular Potentials by Ultrahigh-Resolution Resonant Photoemission andAb InitioCalculations

Theoretical Fine Spectroscopy with SAC-CI Method: Outer- and Inner-Valence Ionization Spectra of CO and N2

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