A valence- and inner-shell electronic and photoelectron spectroscopic study of the frontier orbitals of 2,1,3-benzothiadiazole, C6H4SN2, 1,3,2,4-benzodithiadiazine, C6H4S2N2, and 1,3,5,2,4-benzotrithiadiazepine, C6H4S3N2

Hitchcock, Adam P.; DeWitte, Robert S.; Esbroeck, J.M. Van; Aebi, Philipp; Frenc, C.L.; Oakley, Richard T.; Westwood, N. P. C.

doi:10.1016/0368-2048(91)85021-k

Cited by 37 publications

(11 citation statements)

References 41 publications

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“…Figure shows NEXAFS spectra following sulfur K edge photoexcitation for as-cast PSiF-DBT and thermal-annealed PSiF-DBT-100 and PSiF-DBT-200 films. Feature assignments in the NEXAFS spectra were reported before by Garcia-Basabe et al These spectra are characterized by four features (see inset of Figure ): B1 and B2 signals are attributed to S 1s-π*(S–N) and σ*(S–N) transitions in the benzothiadiazole unit, , while T1 and T2 signals correspond to the S 1s-π* and -σ* transitions at the thiophene unit . This result was corroborated by sulfur inner-shell HF/CI calculations performed for the geometry-optimized PSiF-DBT monomer, as will be discussed below.…”

Section: Resultssupporting

confidence: 75%

Charge Transfer Dynamics and Molecular Orientation Probed by Core Electron Spectroscopies on thermal-annealed Polysilafluorene Derivative: Experimental and Theoretical Approaches

et al. 2014

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Ultrafast charge delocalization dynamics in excited states of internal donor–acceptor copolymer poly[2,7-(9,9-bis(2-ethylhexyl)-dibenzosilole)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole] (PSiF-DBT) was studied by resonant Auger spectroscopy (RAS) measured around silicon and sulfur K edges using the core-hole clock approach. The effect of the thermal annealing treatment at 100 and 200 °C on the charge transfer delocalization times and molecular orientation were probed. Exponential dependence of charge transfer times (τ CT) with photon energy was found at both absorption edges with a decreasing curve slope with the thermal treatment. Features characteristics of the Auger Resonant Raman effect were observed at sulfur KL2,3L2,3 Auger decay spectra. Edge-on and plane-on molecular orientations with respect to the substrate surface were measured for the thiophene and benzothiadiazole units, respectively, using angular-dependent NEXAFS spectra at the S K edge. Molecular orientation of silafluorene was also probed by NEXAFS at the Si K edge. The improvement of the polymer ordering with annealing was evaluated by NEXAFS. Differences in charge transfer times at Si and S K edges may be related to the localized–delocalized character of the molecular orbitals (MOs) involved in those excitation processes, which was corroborated by theoretical calculations at the Hartree–Fock (HF) level, with explicit relaxation of molecular orbitals due to the core-hole. The molecular orientation effect in the charge transfer process was also investigated through the nonadiabatic coupling matrix elements involving the first low-lying excited states in both K edge excitations.

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Section: Resultssupporting

confidence: 75%

Charge Transfer Dynamics and Molecular Orientation Probed by Core Electron Spectroscopies on thermal-annealed Polysilafluorene Derivative: Experimental and Theoretical Approaches

et al. 2014

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“…The 3 main resonant transitions in the TIY spectrum are assigned to the (C1s → π*) type, in agreement with the typical literature assignments for related molecules . As previously discussed, the upper limits for the C1s ionization thresholds have been determined for the thiazole molecule and are also indicated in TIY spectrum in Figure .…”

Section: Discussion and Resultssupporting

confidence: 88%

Photoionization and ionic dissociation of the C₃H₃NS molecule induced by soft X‐ray near the C1s edge

et al. 2017

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Time of flight mass spectrometry, electron-ion coincidence, and ion yield spectroscopy were employed to investigate for the first time the thiazole (C H NS) molecule in the gas phase excited by synchrotron radiation in the soft X-ray domain. Total ion yield (TIY) and photoelectron-photoion coincidence (PEPICO) spectra were recorded as a function of the photon energy in the vicinity of the carbon K edge (C1s). The C1s resonant transitions as well as the core ionization thresholds have been determined from the profile of TIY spectrum, and the features were discussed. The corresponding partial ion yields were determined from the PEPICO spectra for the cation species produced upon the molecular photodissociation. Additional ab initio calculations have also been performed from where relevant structural and electronic configuration parameters were obtained for this molecule.

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“…The PCPDTBT polymer and the 1:1 blend with PCBM were previously studied with X-ray absorption near edge structure. − For the benzothiadiazole and the thiophene molecules, K-edge spectra are available in refs and . X-ray excitation energies denoted by B arise from excitations primarily associated with the benzothiadiazole parts of the polymer, and energy positions denoted by T arise from the thiophene parts. − The point denoted by P is slightly below the core ionization threshold.…”

Section: Resultsmentioning

confidence: 99%

Femtosecond and Attosecond Electron-Transfer Dynamics in PCPDTBT:PCBM Bulk Heterojunctions

et al. 2018

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Charge separation efficiency is a crucial parameter for photovoltaic devicespolymers consisting of alternating electron-rich and electron-deficient parts can achieve high such efficiencies, for instance, together with a fullerene electron acceptor. This offers a viable path toward solar cells with organic bulk heterojunctions. Here, we measured the charge-transfer times in the femtosecond and attosecond regimes via the decay of sulfur 1s X-ray core-excited states (with the core-hole clock method) in blends of a low-band gap polymer {PCPDTBT [poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]]} consisting of a cyclopentadithiophene electron-rich part and a benzothiadiazole electron-deficient part. The constituting parts of the bulk heterojunction were varied by adding the fullerene derivative PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) (weight ratio of polymer/PCBM as 1:0, 1:1, 1:2, and 1:3). For low-energy excitations, the charge-transfer time varies to the largest extent for the thiophene donor part. The charge-transfer time in the 1:2 blend is reduced by 86% compared to that of pristine PCPDTBT. At higher energy excitations, the charge-transfer time does not vary with the chemical environment, as this regime is dominated by intramolecular conduction that yields ultrafast charge-transfer times for all blends, approaching 170 as. We thus demonstrate that the core-hole clock method applied to a series with changing composition can give information about local electron dynamics (with chemical specificity) at interfaces between the constituting partsthe crucial part of a bulk heterojunction where the initial charge separation occurs.

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A valence- and inner-shell electronic and photoelectron spectroscopic study of the frontier orbitals of 2,1,3-benzothiadiazole, C6H4SN2, 1,3,2,4-benzodithiadiazine, C6H4S2N2, and 1,3,5,2,4-benzotrithiadiazepine, C6H4S3N2

Cited by 37 publications

References 41 publications

Charge Transfer Dynamics and Molecular Orientation Probed by Core Electron Spectroscopies on thermal-annealed Polysilafluorene Derivative: Experimental and Theoretical Approaches

Charge Transfer Dynamics and Molecular Orientation Probed by Core Electron Spectroscopies on thermal-annealed Polysilafluorene Derivative: Experimental and Theoretical Approaches

Photoionization and ionic dissociation of the C₃H₃NS molecule induced by soft X‐ray near the C1s edge

Femtosecond and Attosecond Electron-Transfer Dynamics in PCPDTBT:PCBM Bulk Heterojunctions

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A valence- and inner-shell electronic and photoelectron spectroscopic study of the frontier orbitals of 2,1,3-benzothiadiazole, C6H4SN2, 1,3,2,4-benzodithiadiazine, C6H4S2N2, and 1,3,5,2,4-benzotrithiadiazepine, C6H4S3N2

Cited by 37 publications

References 41 publications

Charge Transfer Dynamics and Molecular Orientation Probed by Core Electron Spectroscopies on thermal-annealed Polysilafluorene Derivative: Experimental and Theoretical Approaches

Charge Transfer Dynamics and Molecular Orientation Probed by Core Electron Spectroscopies on thermal-annealed Polysilafluorene Derivative: Experimental and Theoretical Approaches

Photoionization and ionic dissociation of the C3H3NS molecule induced by soft X‐ray near the C1s edge

Femtosecond and Attosecond Electron-Transfer Dynamics in PCPDTBT:PCBM Bulk Heterojunctions

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Photoionization and ionic dissociation of the C₃H₃NS molecule induced by soft X‐ray near the C1s edge