Conformation Dependence of Electronic Structures of Poly(ethylene oxide)

Brena, Barbara; Zhuang, Guorong V.; Augustsson, Andreas; Liu, Gao; Nordgren, Joseph; Guo, Jinghua; Ross, Philip N.; Luo, Yi

doi:10.1021/jp045685u

Cited by 17 publications

(15 citation statements)

References 39 publications

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“…However, it is not trivial to find the molecular confirmation experimentally with the predictions from theory. Peak A is due to O2s atomic orbital, while its higher intensity can be attributed to relatively higher atomic photoionization cross-section (Ref [21]. and Ref.24 therein).…”

Section: Morphological and Electronic Properties Of The Surfacementioning

confidence: 99%

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Tuning the degree of oxidation and electron delocalization of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) with solid-electrolyte

Vempati

Ertaş

Çelebioğlu

et al. 2017

Applied Surface Science

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We report on the effects of ionic interaction on the electronic structure of PEDOT:PSS where the oxidation state of PEDOT is an import aspect for various applications. Additional ionic interactions are introduced and controlled by varying the fraction of poly(ethylene oxide) (PEO). These interactions are balanced against the inherent cohesive forces within each of the polymers constituting intertwined networks. Raman spectra evidenced a peak-shift as high as ∼14 cm −1 for C C vibrational region which suggested increasing degree of oxidation of PEDOT for higher PEO fractions. Changes to the single and bipolaronic absorption bands support the results from the Raman spectra. For highest PEO fraction neutral-PEDOT and lowered bipolaron density is attributed to localization of PEDOT chains within PEO matrix. Interestingly, for higher PEO fractions the electronic density of states (DOS) of HOMO and core-levels (S2p, C1s and O1s) suggested increased degree of oxidation and electron localization on PEDOT. Near and below (∼12 eV) Fermi level, contribution to the O2p and C2p atomic orbitals depicted significantly different DOS. Also we note energetic shift for O2s/C2s and bonding CC atomic and molecular DOS, respectively. The correlation between some surface and bulk-related properties suggests the uniformity of the blend material which might be vital for the application in electrochemical devices.

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Section: Morphological and Electronic Properties Of The Surfacementioning

confidence: 99%

“…For PEO, a low intensity broad feature extends toward the E F . The molecular confirmation (planar zigzag, helix, zigzag I and zigzag II) of PEO is known to determine the DOS [21]. However, it is not trivial to find the molecular confirmation experimentally with the predictions from theory.…”

Section: Morphological and Electronic Properties Of The Surfacementioning

confidence: 99%

Tuning the degree of oxidation and electron delocalization of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) with solid-electrolyte

Vempati

Ertaş

Çelebioğlu

et al. 2017

Applied Surface Science

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“…In a recent study, Zhang et al 50 have shown that the intensity ratio for pyrrole-and benzene-type carbons in the C1s PE spectrum is also photon energy dependent. However, time dependent DFT/PES studies 47,51 have described the shake-up structure of the H 2 Pc and NiPc giving the intensity and the energy position of the benzene and pyrrole related shake-up, contributing to the C1s photoemission spectrum. In the case of H 2 Pc the benzene shakeup, at 286.4 eV binding energy, accounts for 9% of the total intensity of the C1s spectrum recorded by Al K␣ radiation.…”

Section: C1s Photoelectron Spectrummentioning

confidence: 99%

The electronic structure of iron phthalocyanine probed by photoelectron and x-ray absorption spectroscopies and density functional theory calculations

Åhlund

Nilson

Schiessling

et al. 2006

The Journal of Chemical Physics

115

110

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A joint experimental and theoretical work to explain the electronic and geometrical structure of an in situ prepared film of iron phthalocyanine (FePc) on silicon (100) is presented. FePc molecular films have been characterized by core and valence photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS), and the results have been interpreted and simulated by density functional theory (DFT) calculations. C1s and N1s PE spectra have been analyzed by taking into account all chemically nonequivalent C and N atoms in the molecule. In the Fe2p(32) spectra it has been possible to resolve two components that can be related to the open shell structure of the molecule. By valence PES and N1s XAS data, the geometrical orientation of the FePc molecules in the film could be determined. Our results indicate that for the FePc on Si(100), the molecules within the film are mainly standing on the surface. The experimental N1s XAS spectra are very well reproduced by the theoretical calculations, which are both angle and atomic resolved, giving a detailed description of the electronic and geometric structure of the FePc film. Furthermore, the asymmetry and the intensity angle variation of the first N1s XAS threshold feature could be explained by the presented DFT calculations as due to the chemical nonequivalence of the N atoms and the symmetry character of the lowest unoccupied molecular orbital.

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“…At one end of the scale, the various contributions to can be parsed into hypothetical anisotropic monomer tensor components of , positioned and oriented according to a structural model for aPS, and tested against measured scattering. At the other end, ab initio DFT calculations of resonant scattering factors [18,[54][55][56][57][58] of carbon atoms in quantum MD models [59] could be coarse-grained at the functional group, monomer, or larger level and used to calculate scattering. This latter approach can directly explore the extent to which monomer scattering properties are identical and independent of non-bonding chain conformation effects, and to more directly explore the backbone and phenyl contributions to both spatially-averaged reflectivity and spatially-resolved scattering.…”

Section: B Depolarized Scattering From Short-range Orientation Fluctmentioning

confidence: 99%

Molecular anisotropy effects in carbonK-edge scattering: Depolarized diffuse scattering and optical anisotropy

Stone

Kortright

2014

Phys. Rev. B

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Some polymer properties, such as conductivity, are very sensitive to short-and intermediaterange orientational and positional ordering of anisotropic molecular functional groups, and yet means to characterize orientational order in disordered systems are very limited. We demonstrate that resonant scattering at the carbon K-edge is uniquely sensitive to short-range orientation correlations in polymers through depolarized scattering at high momentum transfers, using atactic polystyrene as a well-characterized test system. Depolarized scattering is found to coexist with unpolarized fluorescence, and to exhibit pronounced anisotropy. We also quantify the spatially averaged optical anisotropy from low-angle reflectivity measurements, finding anisotropy consistent with prior visible, x-ray absorption, and theoretical studies. The average anisotropy is much smaller than that in the depolarized scattering and the two have different character. Both measurements exhibit clear spectral signatures from the phenyl rings and the polyethylene-like backbone. Discussion focuses on analysis considerations and prospects for using this depolarized scattering for studies of disorder in soft condensed matter.

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Conformation Dependence of Electronic Structures of Poly(ethylene oxide)

Cited by 17 publications

References 39 publications

Tuning the degree of oxidation and electron delocalization of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) with solid-electrolyte

Tuning the degree of oxidation and electron delocalization of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) with solid-electrolyte

The electronic structure of iron phthalocyanine probed by photoelectron and x-ray absorption spectroscopies and density functional theory calculations

Molecular anisotropy effects in carbonK-edge scattering: Depolarized diffuse scattering and optical anisotropy

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