The intensity ratios of the multiplet-split $\mathrm{N}1s$ peak NO and $\mathrm{O}1s$ ${\mathrm{O}}_{2}$ in x-ray photoemission spectra these paramagnetic molecules were found to exceed simple multiplet $\frac{(S+1)}{S}$. Hartree-Fock calculations performed on ground state $1s$-hole states each case, total overlap probabilities for passive orbitals computed. Positive deviations from obtained, but they smaller than experimental deviations....

The x-ray photoemission molecular orbital spectra of gaseous hydrogen fluoride and the fluorinated methanes (CHn F4−n, 0≥ n ≥4) are reported. Ab initio, Koopman's theorem energies a three-parameter relaxation model were used to fit experimental binding energies. Excellent agreement was obtained. Relative intensities orbitals computed using Gelius with both CNDO/2 ab initio atomic populations. In case results, net populations found be superior gross in reproducing intensities. most cases,...

Views Icon Article contents Figures & tables Video Audio Supplementary Data Peer Review Share Twitter Facebook Reddit LinkedIn Tools Reprints and Permissions Cite Search Site Citation D. W. Davis, J. M. Hollander, A. Shirley, T. Thomas; Comparison of Core‐Level Binding Energy Shifts in Molecules with Predictions Based on Koopmans' Theorem. Chem. Phys. 15 March 1970; 52 (6): 3295–3296. https://doi.org/10.1063/1.1673472 Download citation file: Ris (Zotero) Reference Manager EasyBib Bookends...

Upon impact of a low-energy electron on neutral molecule, an intermediate metastable electron–molecule compound is formed. This species can undergo electron-catalyzed two-bond breaking or cycloelimination, as in the simplest case cyclobutane–ethylene conversion (see scheme). mechanism illustrated for quadricyclanone–norbornadienone cycloelimination reaction using ab initio methods, and its generality appears promising.

Binding-energy shifts of carbon and fluorine 1s levels in small (two to four carbon) fluorinated hydrocarbons are reported. Carbon, nitrogen, oxygen for a number other molecules also All samples were studied as gases: A total 72 new measured. The results analyzed using three electrostatic potential models. First the RPM theory, which includes final-state relaxation, was used. It correctly predicts N(1s) methylamines, relaxation dominant, showing importance considering when comparing unlike...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTX-ray photoelectron spectroscopy of fluorinated benzenesD. W. Davis, David A. Shirley, and T. Darrah ThomasCite this: J. Am. Chem. Soc. 1972, 94, 19, 6565–6575Publication Date (Print):September 1, 1972Publication History Published online1 May 2002Published inissue 1 September 1972https://pubs.acs.org/doi/10.1021/ja00774a001https://doi.org/10.1021/ja00774a001research-articleACS PublicationsRequest reuse permissionsArticle...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTModel for proton affinities and inner-shell electron binding energies based on the Hellmann-Feynman theoremD. William Davis J. Wayne RabalaisCite this: Am. Chem. Soc. 1974, 96, 17, 5305–5310Publication Date (Print):August 1, 1974Publication History Published online1 May 2002Published inissue 1 August 1974https://pubs.acs.org/doi/10.1021/ja00824a002https://doi.org/10.1021/ja00824a002research-articleACS PublicationsRequest reuse permissionsArticle...

The binding energies of selected C, N, O, and F 1s electrons in six paramagnetic molecules were measured by x-ray photoemission. A splitting 1.934(41) eV was observed the N(1s) line NF2, several other splittings remeasured or obtained fitting asymmetric but unresolved lines. Use Mg Kα12 doublet profile improved fits markedly. multiplet hole theory developed to predict final-state splitting. It uses atomic exchange integrals, INDO calculations on an ``equivalent-core'' final state obtain spin...

Bruchrechnung: Langlebige Verbindungszustände mit einem niederenergetischen Elektron und Molekül erfahren im Allgemeinen den Bruch nur einer σ-Bindung bei der ersten Elementarreaktion. Ab-initio-Rechnungen identifizierten nun von gleich vier Bindungen Elementarreaktion: Beim Auftreffen des Elektrons spaltet ein bicyclisches σ-Bindungen in konzertierten weitgehend barrierelosen Schritt.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTHE STABILITY OF HEXA-TERTIARY-ALKYLETHINYLETHANES. THE EFFECT INCREASING WEIGHT ALKYL GROUPSD. W. Davis and C. S. MarvelCite this: J. Am. Chem. Soc. 1931, 53, 10, 3840–3851Publication Date (Print):October 1, 1931Publication History Published online1 May 2002Published inissue 1 October 1931https://pubs.acs.org/doi/10.1021/ja01361a026https://doi.org/10.1021/ja01361a026research-articleACS PublicationsRequest reuse permissionsArticle...

Low energy electrons can initiate and control chemical reactions through resonant attachment forming an electron-molecule compound state. Recently, it has been theoretically shown that free also act as catalysts in reactions. We investigate this novel concept for the case of conversion formic acid into CO2. Resonant production CO2 from cold films by low electron impact is observed using Fourier transform infrared spectroscopy. The peak at 6 eV identified catalytic channel. experimental...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRelative gas-phase acidities and basicities from a proton potential modelD. W. Davis D. A. ShirleyCite this: J. Am. Chem. Soc. 1976, 98, 25, 7898–7903Publication Date (Print):December 1, 1976Publication History Published online1 May 2002Published inissue 1 December 1976https://pubs.acs.org/doi/10.1021/ja00441a002https://doi.org/10.1021/ja00441a002research-articleACS PublicationsRequest reuse permissionsArticle Views45Altmetric-Citations23LEARN...

Ab initio quantum chemical studies show that a very weak molecular complexation of CO2 with dipolar molecule is able to suppress the autoionization electron from its transient negative ion states. Since suppressed, can efficiently relax geometry form reductively activated moiety. Unlike isolated molecules, which are deactivated immediately due their thermodynamic metastability, moieties complexes infinitely long-lived and, hence, permanently reactive.

Following the recent report of first identification methyl acetate (CH3COOCH3) in interstellar medium (ISM), we have carried out vacuum ultraviolet (VUV) and infrared (IR) spectroscopy studies on from 10 K until sublimation an ultrahigh chamber simulating astrochemical conditions. We present VUV IR spectra relevant to ISM Spectral signatures clearly showed molecular reorientation started ice by annealing amorphous formed at K. An irreversible phase change crystalline was found occur between 110 120

Beim Stoß zwischen niederenergetischen Elektronen und einem neutralen Molekül entsteht ein metastabiles Elektron-Molekül-Intermediat, das unter Elektronenkatalyse einen doppelten Bindungsbruch oder eine Cycloeliminierung eingehen kann, wie im einfachsten Fall bei der Umwandlung von Cyclobutan in Ethen (siehe Schema). Der möglicherweise allgemeingültige Mechanismus dieses Prozesses wird für die Quadricyclanon aus Norbornadienon auf Grundlage Ab-initio-Rechnungen erklärt. Detailed facts of...

Using a low energy electron (LEE) as catalyst, the electronic origin of catalytic strategies corresponding to substrate selectivity, reaction specificity and rate enhancement is investigated for reversible unimolecular elementary reaction. An complementarity between catalyst molecule selectivity specificity. The induced by tuning catalyst. maximizes binding forces molecule. Consequently, new electronically metastable high-energy reactant state barrier path are resonantly created specific...

Dissociative electron attachment (DEA) to acetone is studied in terms of the absolute cross section for various fragment channels energy range 0–20 eV. H− found be most dominant followed by O− and OH− with only one resonance peak between 8 9 The DEA dynamics measuring angular distribution kinetic anions using Velocity Slice Imaging technique. fragments suggest a many body break-up lone observed. ab initio calculations show that captured multi-centered anti-bonding molecular orbital which...

Molecular modification induced through the resonant attachment of a low energy electron (LEE) is novel approach for molecular engineering. In this communication, we explore possibility to use LEE as quantum tool in situ preparation short lived molecules. Using ab initio chemical methods, best illustrated intrinsically short-lived carbon-carbon covalent dimer CO from glyoxal molecule. The conversion initiated and driven by capture near 11 eV resulting two-particle one-hole (2p-1h) negative...

The current understanding of photoenzyme-catalyzed [2 + 2] cycloreversion repair cyclobutane pyrimidine dimer (CPD) is that a photogenerated electron from the photolyase enzyme catalyzes repair. This one-electron catalyzed sequential two-bond breaking center and involves negative ion radical as an intermediate. Here, by resonantly capturing two exogenous low-energy electrons into molecular field CPD, we show concerted synchronous reaction, which intermediate-free, hence safe repair, feasible...