Rydberg series of small molecules VIII. Photoelectron spectroscopy and electron spectroscopy of NO<sub>2</sub>

Edqvist, O.; Lindholm, E.; Selin, L.E.; Åsbrink, L.; Kuyatt, C. E.; Mielczarek, S. R.; Simpson, J. A.; Fischer‐Hjalmars, Inga

doi:10.1088/0031-8949/1/4/005

Cited by 65 publications

(37 citation statements)

References 29 publications

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“…͑1.3͒ and ͑1.4͒ M is the (N ϫN ) matrix of the weighted overlap between the densities of the KS orbitals, M k j ϭ͉͐ k (r 1 …”

Section: ͑14͒mentioning

confidence: 99%

“…The theorem can be put in a stronger form, however, in the following way. Consider two KS potentials s (1) and s (2) with their difference ⌬ s ϭ s (2) Ϫ s (1) , the corresponding ground state KS deter-…”

Section: Spin-unrestricted Van Leeuwen and Baerends Proceduresmentioning

confidence: 99%

“…ϫ(r i )(s i )͖ with the densities (1) and (2) , and the density difference ⌬ ϭ (2) Ϫ (1) . We assume that the potentials s (2) and s (1) differ by more than a uniform constant.…”

Section: Spin-unrestricted Van Leeuwen and Baerends Proceduresmentioning

confidence: 99%

“…We assume that the potentials s (2) and s (1) differ by more than a uniform constant. Then, we have from the variation theorem that…”

Section: Spin-unrestricted Van Leeuwen and Baerends Proceduresmentioning

confidence: 99%

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The spin-unrestricted molecular Kohn–Sham solution and the analogue of Koopmans’s theorem for open-shell molecules

Gritsenko

Baerends

2004

The Journal of Chemical Physics

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Spin-unrestricted Kohn-Sham ͑KS͒ solutions are constructed from accurate ab initio spin densities for the prototype doublet molecules NO 2 , ClO 2 , and NF 2 with the iterative local updating procedure of van Leeuwen and Baerends ͑LB͒. A qualitative justification of the LB procedure is given with a ''strong'' form of the Hohenberg-Kohn theorem. The calculated energies i of the occupied KS spin orbitals provide numerical support to the analogue of Koopmans' theorem in spin-density functional theory. In particular, the energies Ϫ i␤ of the minor spin ͑␤͒ valence orbitals of the considered doublet molecules correspond fairly well to the experimental vertical ionization potentials ͑VIPs͒ I i 1 to the triplet cationic states. The energy Ϫ H␣ of the highest occupied ͑spin-unpaired͒ ␣ orbital is equal to the first VIP I H 0 to the singlet cationic state. In turn, the energies Ϫ i␣ of the major spin ͑␣͒ valence orbitals of the closed subshells correspond to a fifty-fifty average of the experimental VIPs I i 1 and I i 0 to the triplet and singlet states. For the Li atom we find that the exact spin densities are represented by a spin-polarized Kohn-Sham system which is not in its ground state, i.e., the orbital energy of the lowest unoccupied ␤ spin orbital is lower than that of the highest occupied ␣ spin orbital ͑''a hole below the Fermi level''͒. The addition of a magnetic field in the Ϫz direction will shift the ␤ levels up so as to restore the Aufbau principle. This is an example of the nonuniqueness of the mapping of the spin density on the KS spin-dependent potentials discussed recently in the literature. The KS potentials may no longer go to zero at infinity, and it is in general the differences s (ϱ)Ϫ i that can be interpreted as ͑averages of͒ ionization energies. In total, the present results suggest the spin-unrestricted KS theory as a natural one-electron independent-particle model for interpretation and assignment of the experimental photoelectron spectra of open-shell molecules.

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“…͑1.3͒ and ͑1.4͒ M is the (N ϫN ) matrix of the weighted overlap between the densities of the KS orbitals, M k j ϭ͉͐ k (r 1 …”

Section: ͑14͒mentioning

confidence: 99%

Section: Spin-unrestricted Van Leeuwen and Baerends Proceduresmentioning

confidence: 99%

“…ϫ(r i )(s i )͖ with the densities (1) and (2) , and the density difference ⌬ ϭ (2) Ϫ (1) . We assume that the potentials s (2) and s (1) differ by more than a uniform constant.…”

Section: Spin-unrestricted Van Leeuwen and Baerends Proceduresmentioning

confidence: 99%

“…We assume that the potentials s (2) and s (1) differ by more than a uniform constant. Then, we have from the variation theorem that…”

Section: Spin-unrestricted Van Leeuwen and Baerends Proceduresmentioning

confidence: 99%

See 2 more Smart Citations

The spin-unrestricted molecular Kohn–Sham solution and the analogue of Koopmans’s theorem for open-shell molecules

Gritsenko

Baerends

2004

The Journal of Chemical Physics

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“…The neighboring line (p4) at 406.01-eV photon energy, also well resolved in the TIY and the ARIY [I(90 • )] spectra, has been proposed to be a further vibrational component of the N t 1s −1 3pπ Rydberg state [16], and was recently assigned as the N t 1s −1 3pπ (001) line [22]. The vibrational assignment for N t 1s −1 excitations made by Prince et al [22] was generally guided by the vibrational energy spacing from valence band photoemission data of the ECM molecule NO 2 [42]. We would rather use the frequency values of the N 2 O neutral ground state as a guide for the vibrational assignment.…”

Section: Resultsmentioning

confidence: 99%

Symmetry and vibrationally resolved absorption spectra near theN Kedges ofN2O: Experiment and theory

et al. 2011

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This is the published version of a paper published in Physical Review A. Atomic, Molecular, and Optical Physics. Citation for the original published paper (version of record):Ehara, M., Horikawa, T., Fukuda, R., Nakatsuji, H., Tanaka, T. et al. (2011) Symmetry and vibrationally resolved absorption spectra near the N K edges of N2O: experiment and theory.Physical Review A. Atomic, Molecular, and Optical Physics, 83(6) In this study, angle-resolved energetic-ion yield spectra were measured in the N 1s excitation region of N 2 O. A Franck-Condon analysis based on ab initio two-dimensional potential energy surfaces of the coreexcited Rydberg states, which were calculated by the symmetry-adapted cluster-configuration interaction method, reproduced observed vibrational excitations specific to the individual Rydberg states well and enabled quantitative assignments. Geometric changes in the terminal nitrogen N t 1s and the central nitrogen N c 1s excited states with respect to the 3pπ , 3pσ , and 4sσ transitions were analyzed. The coupling of these valence and Rydbergs states was examined based on the second moment analysis. Irregular Rydberg-state behavior in the N c 1s −1 4sσ state was observed.

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Photochemical Decay Reactions of N₂O₅, HNO₃, CINO₃ and BrNO₃ in the Energy Range 10–20 eV

Jochims

Denzer

Baumgärtel

et al. 1992

Ber Bunsenges Phys Chem

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The photochemical behaviour of gaseous N2O5, HNO3, CINO3 and BrNO3 has been investigated in the energy range 10–20 eV by photoionization mass spectrometry using monochromatized synchrotron radiation. The decay reactions are analyzed using the photoion yield curves of fragment ions and their appearance energies. Hitherto unknown photochemical reactions and thermochemical data have been evaluated.

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Rydberg series of small molecules VIII. Photoelectron spectroscopy and electron spectroscopy of NO₂

Cited by 65 publications

References 29 publications

The spin-unrestricted molecular Kohn–Sham solution and the analogue of Koopmans’s theorem for open-shell molecules

The spin-unrestricted molecular Kohn–Sham solution and the analogue of Koopmans’s theorem for open-shell molecules

Symmetry and vibrationally resolved absorption spectra near theN Kedges ofN2O: Experiment and theory

Photochemical Decay Reactions of N₂O₅, HNO₃, CINO₃ and BrNO₃ in the Energy Range 10–20 eV

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Rydberg series of small molecules VIII. Photoelectron spectroscopy and electron spectroscopy of NO2

Cited by 65 publications

References 29 publications

The spin-unrestricted molecular Kohn–Sham solution and the analogue of Koopmans’s theorem for open-shell molecules

The spin-unrestricted molecular Kohn–Sham solution and the analogue of Koopmans’s theorem for open-shell molecules

Symmetry and vibrationally resolved absorption spectra near theN Kedges ofN2O: Experiment and theory

Photochemical Decay Reactions of N2O5, HNO3, CINO3 and BrNO3 in the Energy Range 10–20 eV

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Rydberg series of small molecules VIII. Photoelectron spectroscopy and electron spectroscopy of NO₂

Photochemical Decay Reactions of N₂O₅, HNO₃, CINO₃ and BrNO₃ in the Energy Range 10–20 eV