Dependence of the electronic structure on the chain geometry in stereoregular polypropylene: An exploratory theoretical study

Flamant, I.; Mosley, David H.; Deleuze, Michaël S.; André, J. M.; Delhalle, Joseph

doi:10.1002/qua.560520843

Cited by 12 publications

(9 citation statements)

References 25 publications

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“…These signatures have been shown [12][13][14][15] to relate to a mixing of the C 2s and C 2p + H 1s states at the border of the inner and outer valence bands, as a result of long-range methylenic hyperconjugation interactions developing over zigzag planar segments or related structures. XPS measurements on thin films and microcrystalline lamellae of polyethylene have confirmed 16 these findings and impelled further investigations on polypropylene, 17 or gaseous samples 9 of n-pentane, n-hexane, cyclopentane and cyclohexane.…”

Section: Introductionmentioning

confidence: 85%

“…Along the lines of these studies, − this work aims at an evaluation of the potential of photoelectron spectroscopies in the elucidation of the molecular structure of organic surfaces. For this purpose, we consider here self-assembled monolayers of alkanethiols, which from their well-defined composition, thickness, and molecular structure, , provide particularly well-suited reference samples.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Surface Molecular Structure of Self-Assembled Alkanethiols Evidenced by UPS and Photoemission with Synchrotron Radiation

Duwez¹,

Paolo²,

Ghijsen³

et al. 1997

J. Phys. Chem. B

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With the aim of investigating the configurational and conformational characteristics of monolayers of alkanethiols on gold by means of a photoemission experiment, we compare the valence data obtained from these layers using synchrotron radiation and ultraviolet photoemission spectroscopy (UPS). The incident energy used for synchrotron radiation has been chosen very close to the Cooper minimum of the 5d levels of gold, in order to limit as much as possible interference from the substrate. The recorded spectra differ markedly from one sample to another, notwithstanding their closely related chemical nature. These variations are compared consistently with semiquantitative simulations on model clusters and found thereby to reflect specifically the influence of the connectivity and of specific interactions on the electronic structure of long hydrocarbon chains.

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Section: Introductionmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Surface Molecular Structure of Self-Assembled Alkanethiols Evidenced by UPS and Photoemission with Synchrotron Radiation

Duwez¹,

Paolo²,

Ghijsen³

et al. 1997

J. Phys. Chem. B

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“…The parameters commonly adopted are d CC ϭ1.54 Å, d CH ϭ1.09 Å, and bond angles derived from tetrahedral values. An example is the recent exploratory study of single chains of isotactic and two syndiotactic forms of polypropylene, using Hartree-Fock methods 25 to determine the total energies and the energy eigenvalue spectra. Immirzi and Iannelli 26 have used a fiber whole-pattern refinement to analyze x-ray diffraction data.…”

Section: B Isotactic Polypropylenementioning

confidence: 99%

Density functional study of polypropylene and its submolecules

Borrmann¹,

Montanari²,

Jones³

1997

The Journal of Chemical Physics

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Articles you may be interested in Density functional theory study of self-association of N -methylformamide and its effect on intramolecular and intermolecular geometrical parameters and the cis/trans population A density functional study of crystalline acetic acid and its proton transfer polymorphic forms A density functional theory study of vibrational coupling between ribose and base rings of nucleic acids with ribosyl guanosine as a model system Previous density functional ͑DF͒ calculations of the structures of small hydrocarbon molecules ͑CH, CH 2 , C 2 H 2 , C 2 H 4 , C 3 H 6 , C 3 H 8 ) have been extended to larger systems. The structure of a single chain of isotactic polypropylene (it-PP͒ has been optimized, and calculations have been performed for smaller molecules with closely related structures ͑propane C 3 H 8 , several conformers of isopentane C 5 H 12 , and 2,4,6-trimethyl heptane C 10 H 22 ) using both local spin density ͑LSD͒ and non-local ͑gradient-corrected͒ energy functionals. The pronounced transferability of the local structural parameters between C 5 H 12 , C 10 H 22 and it-PP suggests that the energy surfaces calculated for molecules with five carbon atoms should provide a very good representation of the local energy variations in much larger systems.

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“…Firstly, investigations on quasiparticle grounds of the electron binding energies of saturated hydrocarbons of varying size and complexity [6][7][8][9][10] have disclosed evidence for a mixing of the C 2s and C 2p ϩH 1s character of orbitals at the border of the inner and outer valence regions ͑14-22 eV͒. This phenomenon relates to long-range methylenic hyperconjugation in large zigzag planar n-alkane segments, 6,7 and leads to a strong dependence of the ionization spectrum to the conformation of chains.…”

Section: Introductionmentioning

confidence: 99%

Valence electron momentum spectroscopy of n-butane

Wen-Ning

Gao

Ruan

et al. 2000

The Journal of Chemical Physics

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Articles you may be interested inElectron momentum spectroscopy study of Jahn-Teller effect in cyclopropane J. Chem. Phys. 130, 054302 (2009); 10.1063/1.3068619Study of the molecular structure, ionization spectrum, and electronic wave function of 1,3-butadiene using electron momentum spectroscopy and benchmark Dyson orbital theories An investigation of valence shell orbital momentum profiles of difluoromethane by binary (e,2e) spectroscopyThe valence electronic structure and momentum-space electron density distributions of n-butane have been studied by means of high-resolution (e,2e) electron momentum spectroscopy based on noncoplanar symmetric kinematics. Ionization spectra for the range of binding energies 6 to 32 eV and momenta described by azimuthal angles ϭ0°, 2°, 4°, 6°, 8°, and 10°have been recorded and compared to the results of one-particle Green's function calculations, performed using the third-order algebraic-diagrammatic construction ͓ADC͑3͔͒ approximation and series of basis sets of improving quality. Experimental electron momentum profiles have been determined from a set of 11 measurements and compared to theoretical results. It has been shown that despite the complex structure of the spectral bands and the conformational versatility of n-butane, the experimental electron momentum distributions are accurately described by the momentum-space form of orbital densities obtained from Becke three-parameter Lee-Yang-Parr ͑B3LYP͒ density functional calculations. Significant broadening of the spectral lines and the s-type angular dependence of their intensities above 24 eV have been explained by the breakdown of the one-electron picture of ionization for the 3a g molecular orbital.

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Dependence of the electronic structure on the chain geometry in stereoregular polypropylene: An exploratory theoretical study

Cited by 12 publications

References 25 publications

Surface Molecular Structure of Self-Assembled Alkanethiols Evidenced by UPS and Photoemission with Synchrotron Radiation

Surface Molecular Structure of Self-Assembled Alkanethiols Evidenced by UPS and Photoemission with Synchrotron Radiation

Density functional study of polypropylene and its submolecules

Valence electron momentum spectroscopy of n-butane

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