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  • 1
    Online Resource
    Online Resource
    AIP Publishing ; 2010
    In:  The Journal of Chemical Physics Vol. 132, No. 20 ( 2010-05-28)
    In: The Journal of Chemical Physics, AIP Publishing, Vol. 132, No. 20 ( 2010-05-28)
    Abstract: We report cross sections for low-energy elastic electron scattering by pyrrole, obtained with the Schwinger multichannel method implemented with pseudopotentials. Our calculations indicate π∗ shape resonances in the B1 and A2 symmetries, and two σ∗ resonances in the A1 symmetry (the system belongs to the C2v point group). The present assignments of π∗ resonances are very close to those previously reported for the isoelectronic furan molecule, in agreement with electron transmission spectra. The lowest-lying σ∗ anion is localized on the N–H bond and provides a dissociation coordinate similar to those found in the hydroxyl groups of organic acids and alcohols. This σNH∗ resonance overlaps the higher-lying π∗ resonance (possibly both π∗ states) and could give rise to direct and indirect dissociation pathways, which arise from electron attachment to σ∗ and π∗ orbitals, respectively. The photochemistry of pyrrole and 9-H adenine is similar, in particular with respect to the photostability mechanism that allows for the dissipation of the photon energy, and we believe pyrrole would also be a suitable prototype for studies of dissociative electron attachment (DEA) to DNA bases. We point out the connection between the mechanisms of photostability and DEA since both arise from the occupation of σ∗ and π∗ orbitals in neutral excited states and in anion states, respectively.
    Type of Medium: Online Resource
    ISSN: 0021-9606 , 1089-7690
    Language: English
    Publisher: AIP Publishing
    Publication Date: 2010
    detail.hit.zdb_id: 3113-6
    detail.hit.zdb_id: 1473050-9
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  • 2
    Online Resource
    Online Resource
    AIP Publishing ; 1984
    In:  The Journal of Chemical Physics Vol. 80, No. 2 ( 1984-01-15), p. 730-734
    In: The Journal of Chemical Physics, AIP Publishing, Vol. 80, No. 2 ( 1984-01-15), p. 730-734
    Abstract: Pentacarbonyliron sorbed in low density polyethylene (LDPE) or polytetrafluorethylene (PTFE) and irradiated with UV light has been studied by infrared and Mössbauer spectroscopies. The main photofragment reacts with the residual pentacarbonyliron leading to the formation of Fe2(CO)9. This reaction, plus the information obtained from infrared and Mössbauer spectra, suggest that the new species could be assigned as tetracarbonyliron Fe(CO)4 and tricarbonyliron Fe(CO)3. We have proved that molecules sorbed in a polymer matrix can be used as Mössbauer absorbers at low temperature. The polymer matrix allowed the isolation of otherwise unstable species: The high permeability of LDPE to gaseous carbon monoxide precludes the reformation of pentacarbonyliron molecules, thus excluding the ‘‘cage effect’’ observed in frozen gas matrices.
    Type of Medium: Online Resource
    ISSN: 0021-9606 , 1089-7690
    Language: English
    Publisher: AIP Publishing
    Publication Date: 1984
    detail.hit.zdb_id: 3113-6
    detail.hit.zdb_id: 1473050-9
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  • 3
    In: The Journal of Chemical Physics, AIP Publishing, Vol. 142, No. 10 ( 2015-03-14)
    Abstract: We report theoretical and experimental total cross sections for electron scattering by phenol (C6H5OH). The experimental data were obtained with an apparatus based in Madrid and the calculated cross sections with two different methodologies, the independent atom method with screening corrected additivity rule (IAM-SCAR), and the Schwinger multichannel method with pseudopotentials (SMCPP). The SMCPP method in the Nopen-channel coupling scheme, at the static-exchange-plus-polarization approximation, is employed to calculate the scattering amplitudes at impact energies ranging from 5.0 eV to 50 eV. We discuss the multichannel coupling effects in the calculated cross sections, in particular how the number of excited states included in the open-channel space impacts upon the convergence of the elastic cross sections at higher collision energies. The IAM-SCAR approach was also used to obtain the elastic differential cross sections (DCSs) and for correcting the experimental total cross sections for the so-called forward angle scattering effect. We found a very good agreement between our SMCPP theoretical differential, integral, and momentum transfer cross sections and experimental data for benzene (a molecule differing from phenol by replacing a hydrogen atom in benzene with a hydroxyl group). Although some discrepancies were found for lower energies, the agreement between the SMCPP data and the DCSs obtained with the IAM-SCAR method improves, as expected, as the impact energy increases. We also have a good agreement among the present SMCPP calculated total cross section (which includes elastic, 32 inelastic electronic excitation processes and ionization contributions, the latter estimated with the binary-encounter-Bethe model), the IAM-SCAR total cross section, and the experimental data when the latter is corrected for the forward angle scattering effect [Fuss et al., Phys. Rev. A 88, 042702 (2013)].
    Type of Medium: Online Resource
    ISSN: 0021-9606 , 1089-7690
    Language: English
    Publisher: AIP Publishing
    Publication Date: 2015
    detail.hit.zdb_id: 3113-6
    detail.hit.zdb_id: 1473050-9
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  • 4
    In: The Journal of Chemical Physics, AIP Publishing, Vol. 141, No. 5 ( 2014-08-07)
    Abstract: We report on the shape resonance spectra of phenol-water clusters, as obtained from elastic electron scattering calculations. Our results, along with virtual orbital analysis, indicate that the well-known indirect mechanism for hydrogen elimination in the gas phase is significantly impacted on by microsolvation, due to the competition between vibronic couplings on the solute and solvent molecules. This fact suggests how relevant the solvation effects could be for the electron-driven damage of biomolecules and the biomass delignification [E. M. de Oliveira et al., Phys. Rev. A 86, 020701(R) (2012)]. We also discuss microsolvation signatures in the differential cross sections that could help to identify the solvated complexes and access the composition of gaseous admixtures of these species.
    Type of Medium: Online Resource
    ISSN: 0021-9606 , 1089-7690
    Language: English
    Publisher: AIP Publishing
    Publication Date: 2014
    detail.hit.zdb_id: 3113-6
    detail.hit.zdb_id: 1473050-9
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  • 5
    Online Resource
    Online Resource
    AIP Publishing ; 2015
    In:  The Journal of Chemical Physics Vol. 142, No. 14 ( 2015-04-14)
    In: The Journal of Chemical Physics, AIP Publishing, Vol. 142, No. 14 ( 2015-04-14)
    Abstract: The thermodynamics and kinetics of the one dimensional lattice gas with repulsive interaction are investigated using transfer matrix technique and Monte Carlo simulations. This simple model is shown to exhibit waterlike anomalies in density, thermal expansion coefficient, and self-diffusion. An unified description for the thermodynamic anomalies in this model is achieved based on the ground state residual entropy which appears in the model due to mixing entropy in a ground state phase transition.
    Type of Medium: Online Resource
    ISSN: 0021-9606 , 1089-7690
    Language: English
    Publisher: AIP Publishing
    Publication Date: 2015
    detail.hit.zdb_id: 3113-6
    detail.hit.zdb_id: 1473050-9
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  • 6
    Online Resource
    Online Resource
    AIP Publishing ; 2011
    In:  The Journal of Chemical Physics Vol. 134, No. 2 ( 2011-01-14)
    In: The Journal of Chemical Physics, AIP Publishing, Vol. 134, No. 2 ( 2011-01-14)
    Abstract: We investigate the occurrence of waterlike thermodynamic and dynamic anomalous behavior in a one dimensional lattice gas model. The system thermodynamics is obtained using the transfer matrix technique and anomalies on density and thermodynamic response functions are found. When the hydrogen bond (molecules separated by holes) is more attractive than the van der Waals interaction (molecules in contact) a transition between two fluid structures is found at null temperature and high pressure. This transition is analogous to a ‘critical point’ and intimately connects the anomalies in density and in thermodynamic response functions. Monte Carlo simulations were performed in the neighborhood of this transition and used to calculate the self diffusion constant, which increases with density as in liquid water.
    Type of Medium: Online Resource
    ISSN: 0021-9606 , 1089-7690
    Language: English
    Publisher: AIP Publishing
    Publication Date: 2011
    detail.hit.zdb_id: 3113-6
    detail.hit.zdb_id: 1473050-9
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  • 7
    In: Journal of Applied Physics, AIP Publishing, Vol. 110, No. 4 ( 2011-08-15)
    Abstract: The importance of interface effects for organic devices has long been recognized, but getting detailed knowledge of the extent of such effects remains a major challenge because of the difficulty in distinguishing from bulk effects. This paper addresses the interface effects on the emission efficiency of poly(p-phenylene vinylene) (PPV), by producing layer-by-layer (LBL) films of PPV alternated with dodecylbenzenesulfonate. Films with thickness varying from ∼15 to 225 nm had the structural defects controlled empirically by converting the films at two temperatures, 110 and 230 °C, while the optical properties were characterized by using optical absorption, photoluminescence (PL), and photoluminescence excitation spectra. Blueshifts in the absorption and PL spectra for LBL films with less than 25 bilayers ( & lt;40–50 nm) pointed to a larger number of PPV segments with low conjugation degree, regardless of the conversion temperature. For these thin films, the mean free-path for diffusion of photoexcited carriers decreased, and energy transfer may have been hampered owing to the low mobility of the excited carriers. The emission efficiency was then found to depend on the concentration of structural defects, i.e., on the conversion temperature. For thick films with more than 25 bilayers, on the other hand, the PL signal did not depend on the PPV conversion temperature. We also checked that the interface effects were not caused by waveguiding properties of the excited light. Overall, the electronic states at the interface were more localized, and this applied to film thickness of up to 40–50 nm. Because this is a typical film thickness in devices, the implication from the findings here is that interface phenomena should be a primary concern for the design of any organic device.
    Type of Medium: Online Resource
    ISSN: 0021-8979 , 1089-7550
    Language: English
    Publisher: AIP Publishing
    Publication Date: 2011
    detail.hit.zdb_id: 220641-9
    detail.hit.zdb_id: 3112-4
    detail.hit.zdb_id: 1476463-5
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