Structural impact on the methano bridge in norbornadiene, norbornene and norbornane

Wang, Feng; Brunger, M. J.; Winkler, David A.

doi:10.1016/j.jpcs.2004.08.018

Cited by 12 publications

(8 citation statements)

References 41 publications

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“…The present study is the final in a series that looked at the chemically similar molecules NBD, NBN, and NBA . Although a preliminary report into how the valence electronic structure of these molecules changes as the double bonds of NBD are progressively saturated has been made, a detailed analysis of the sensitivity of the respective momentum distributions to these bonding changes has yet to be made. Such a review is foreshadowed here, although no further details are given at this time.…”

Section: Discussionmentioning

confidence: 99%

“…In light of the marginal agreement between the DFT and experimental ionization energies that we described earlier, further calculations employing more sophisticated Green's function techniques were undertaken. These calculations, described in detail in the next section, are all based on geometries 9 that have been optimized using density functional theory 43 employing the TZVP basis set and the nonlocal hybrid Becke three-parameter Lee-Yang-Parr functional (B3LYP). 30,48…”

Section: Theoretical Analysis Of Ems Cross Sectionsmentioning

confidence: 99%

“…The results are summarized in Table 3. Note that in Table 3 we have only included the highest-level calculation reported by Holthausen and Koch 82 and have omitted the recent calculations on the structural impact on the methano-ring in norbornadiene, norbornene, and norbornane by Wang et al 9 as they originate from our group. To assist the reader in the discussion that follows, refer to the structural representation and atom numbering of the norbornene molecule that we gave in Figure 1.…”

Section: Molecular Properties Of Norbornenementioning

confidence: 99%

“…We used the BP/TZVP model to derive the molecular structure of norbornene. This was compared in detail with experimentally determined values − and those from other MO calculations ,,, to determine how well the BP/TZVP model reproduced the structure.…”

Section: Molecular Properties Of Norbornenementioning

confidence: 99%

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Investigation into the Valence Electronic Structure of Norbornene Using Electron Momentum Spectroscopy, Green's Function, and Density Functional Theories

et al. 2005

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Results of a study of the valence electronic structure of norbornene (C(7)H(10)), up to binding energies of 30 eV, are reported. Experimental electron momentum spectroscopy (EMS) and theoretical Green's function and density functional theory approaches were utilized in this investigation. A stringent comparison between the electron momentum spectroscopy and theoretical orbital momentum distributions found that, among the tested models, the combination of the Becke-Perdew functional and a polarized valence basis set of triple-zeta quality provides the best representation of the electron momentum distributions for all 19 valence orbitals of norbornene. This experimentally validated model was then used to extract other molecular properties of norbornene (geometry, infrared spectrum). When these calculated properties are compared to corresponding results from independent measurements, reasonable agreement is typically found. Due to the improved energy resolution, EMS is now at a stage to very finely image the effective topology of molecular orbitals at varying distances from the molecular center, and the way the individual atomic components interact with each other, often in excellent agreement with theory. This will be demonstrated here. Green's Function calculations employing the third-order algebraic diagrammatic construction scheme indicate that the orbital picture of ionization breaks down at binding energies larger than about 22 eV. Despite this complication, they enable insights within 0.2 eV accuracy into the available ultraviolet emission and newly presented (e,2e) ionization spectra. Finally, limitations inherent to calculations of momentum distributions based on Kohn-Sham orbitals and employing the vertical depiction of ionization processes are emphasized, in a formal discussion of EMS cross sections employing Dyson orbitals.

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Section: Discussionmentioning

confidence: 99%

Section: Theoretical Analysis Of Ems Cross Sectionsmentioning

confidence: 99%

Section: Molecular Properties Of Norbornenementioning

confidence: 99%

Section: Molecular Properties Of Norbornenementioning

confidence: 99%

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Investigation into the Valence Electronic Structure of Norbornene Using Electron Momentum Spectroscopy, Green's Function, and Density Functional Theories

et al. 2005

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“…It is our thesis that by unraveling the electronic structure of norbornane using EMS in conjunction with DFT calculations and the 1p-GF theory of ionization, we may probe the influence of substantial cyclic strains on chemical bonds. In this respect we note our preliminary study 17 on all three molecules I-III, a paper which arose from an invited presentation at the Sagamore 14th meeting.…”

Section: Introductionmentioning

confidence: 98%

Norbornane: An investigation into its valence electronic structure using electron momentum spectroscopy, and density functional and Green’s function theories

Knippenberg

Nixon

Brunger

et al. 2004

The Journal of Chemical Physics

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We report on the results of an exhaustive study of the valence electronic structure of norbornane (C 7 H 12 ), up to binding energies of 29 eV. Experimental electron momentum spectroscopy and theoretical Green's function and density functional theory approaches were all utilized in this investigation. A stringent comparison between the electron momentum spectroscopy and theoretical orbital momentum distributions found that, among all the tested models, the combination of the Becke-Perdew functional and a polarized valence basis set of triple-quality provides the best representation of the electron momentum distributions for all of the 20 valence orbitals of norbornane. This experimentally validated quantum chemistry model was then used to extract some chemically important properties of norbornane. When these calculated properties are compared to corresponding results from other independent measurements, generally good agreement is found. Green's function calculations with the aid of the third-order algebraic diagrammatic construction scheme indicate that the orbital picture of ionization breaks down at binding energies larger than 22.5 eV. Despite this complication, they enable insights within 0.2 eV accuracy into the available ultraviolet photoemission and newly presented (e,2e) ionization spectra, except for the band associated with the 1a 2 Ϫ1 one-hole state, which is probably subject to rather significant vibronic coupling effects, and a band at ϳ25 eV characterized by a momentum distribution of ''s-type'' symmetry, which Green's function calculations fail to reproduce. We note the vicinity of the vertical double ionization threshold at ϳ26 eV.

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Orbital based electronic structural signatures of the guanine keto G-7H/G-9H tautomer pair as studied using dual space analysis

Jones

Wang

Winkler

et al. 2006

Biophysical Chemistry

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Structural impact on the methano bridge in norbornadiene, norbornene and norbornane

Cited by 12 publications

References 41 publications

Investigation into the Valence Electronic Structure of Norbornene Using Electron Momentum Spectroscopy, Green's Function, and Density Functional Theories

Investigation into the Valence Electronic Structure of Norbornene Using Electron Momentum Spectroscopy, Green's Function, and Density Functional Theories

Norbornane: An investigation into its valence electronic structure using electron momentum spectroscopy, and density functional and Green’s function theories

Orbital based electronic structural signatures of the guanine keto G-7H/G-9H tautomer pair as studied using dual space analysis

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