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- Carroll, Thomas X., et al.
(författare)
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Fluorine as a π donor. Carbon 1s photoelectron spectroscopy and proton affinities of fluorobenzenes
- 2006
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Ingår i: Journal of Organic Chemistry. - : American Chemical Society (ACS). - 0022-3263 .- 1520-6904. ; 71:5, s. 1961-1968
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Tidskriftsartikel (refereegranskat)abstract
- The carbon 1s ionization energies for all of the carbon atoms in 10 fluorine-substituted benzene molecules have been measured by high-resolution photoelectron spectroscopy. A total of 30 ionization energies can be accurately described by an additivity model with four parameters that describe the effect of a fluorine that is ipso, ortho, meta, or para to the site of ionization. A similar additivity relationship describes the enthalpies of protonation. The additivity parameters reflect the role of fluorine as an electron-withdrawing group and as a π-electron donating group. The ionization energies and proton affinities correlate linearly, but there are four different correlations depending on whether there are 0, 1, 2, or 3 fluorines ortho or para to the site of ionization or protonation. That there are four correlation lines can be understood in terms of the ability of the hydrogens at the site of protonation to act as a π-electron acceptor. A comparison of the ionization energies and proton affinities, together with the results of electronic structure calculations, gives insight into the effects of fluorine as an electron-withdrawing group and as a π donor, both in the neutral molecule and in response to an added positive charge.
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- Ottosson, Niklas, et al.
(författare)
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On the Origins of Core-Electron Chemical Shifts of Small Biomolecules in Aqueous Solution : Insights from Photoemisson and ab Initio Calculations of Glycine(aq)
- 2011
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society. - 0002-7863 .- 1520-5126. ; 133:9, s. 3120-3130
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Tidskriftsartikel (refereegranskat)abstract
- The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon is binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak widths) are related to the details of the hydrogen bond configurations, i.e. the geometries of the water solvation shell and the associated electronic screening. The comparison between the experiments and calculations further enables the separation of protonation-induced (covalent) and solvent-induced (electrostatic) screening contributions to the chemical shifts in the aqueous phase. The present core-level line shape analysis facilitates an accurate interpretation of photoelectron spectra from larger biomolecular solutes than glycine.
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- Rosso, Aldana, et al.
(författare)
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The role of molecular polarity in cluster local structure studied by photoelectron spectroscopy
- 2007
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 435:1-3, s. 79-83
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the spatial structure and electronic levels of clusters of the molecule CH3Br to investigate the effects of molecular polarity on these properties. Analysis of the core level photoelectron spectra of initially neutral CH3Br clusters shows that the C 1 s-1 state has a 30% larger binding energy shift between free molecules and clusters than the Br 3d-1 state. This difference is attributed to an anti-parallel packing of the molecules induced by the polar character of bromomethane. The results obtained from the analysis of valence cluster spectra also support the proposed structure.
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- Travnikova, Oksana, et al.
(författare)
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Energy-Dependent Relative Cross Sections in Carbon 1s Photoionization : Separation of Direct Shake and Inelastic Scattering Effects in Single Molecules
- 2019
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Ingår i: Journal of Physical Chemistry A. - : AMER CHEMICAL SOC. - 1089-5639 .- 1520-5215. ; 123:35, s. 7619-7635
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrate that the possibility of monitoring relative photoionization cross sections over a large photon energy range allows us to study and disentangle shake processes and intramolecular inelastic scattering effects. In this gas-phase study, relative intensities of the carbon 1s photoelectron lines from chemically inequivalent carbon atoms in the same molecule have been measured as a function of the incident photon energy in the range of 300-6000 eV. We present relative cross sections for the chemically shifted carbon 1s lines in the photoelectron spectra of ethyl trifluoroacetate (the "ESCA" molecule). The results are compared with those of methyl trifluoroacetate and S-ethyl trifluorothioacetate as well as a series of chloro-substituted ethanes and 2-butyne. In the soft X-ray energy range, the cross sections show an extended X-ray absorption fine structure type of wiggles, as was previously observed for a series of chloroethanes. The oscillations are damped in the hard X-ray energy range, but deviations of cross-section ratios from stoichiometry persist, even at high energies. The current findings are supported by theoretical calculations based on a multiple scattering model. The use of soft and tender X-rays provides a more complete picture of the dominant processes accompanying photoionization. Such processes reduce the main photoelectron line intensities by 20-60%. Using both energy ranges enabled us to discern the process of intramolecular inelastic scattering of the outgoing electron, whose significance is otherwise difficult to assess for isolated molecules. This effect relates to the notion of the inelastic mean free path commonly used in photoemission studies of clusters and condensed matter.
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- Travnikova, Oksana, et al.
(författare)
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The ESCA molecule-Historical remarks and new results
- 2012
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 185:8-9, s. 191-197
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Tidskriftsartikel (refereegranskat)abstract
- The C is photoelectron spectrum of ethyl trifluoroacetate (CF3-CO-O-CH2-CH3), also known as the 'ESCA molecule', is the most illustrative showcase of chemical shifts in photoelectron spectroscopy. The binding energies of the four carbon atoms of this molecule spread over more than 8 eV with energy separations ranging from 1.7 to 3.1 eV owing to different chemical environments and hence different charge states of these atoms. The paper discusses history and importance of this spectrum in the field of photoelectron spectroscopy starting from the time of invention of the ESCA technique. The main focus of the paper is a 'revisit' of this spectrum using the most modern experimental and computational tools. Large geometrical changes, different for each ionization site, and the presence of two conformers of ethyl trifluoroacetate influence the spectral lineshapes of all four C 1s lines. These effects are carefully modeled by theory and investigated in the experimental spectrum.
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