BF<sub>3</sub> Valence and Rydberg States As Probed by Electron Energy Loss Spectroscopy and <i>ab Initio</i> Calculations

Duflot, Denis; Hoshino, M.; Limão-Vieira, P.; Suga, A.; Kato, H.; Tanaka, Hiroshi

doi:10.1021/jp509375y

Cited by 6 publications

(3 citation statements)

References 49 publications

(112 reference statements)

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“…A careful inspection of Figure c reveals that the spectrum of isolated BF 3 does not exhibit any absorption feature in the region between 2.5 and 8.0 eV, considered in this analysis. The absorption onset of this molecule is found at 12.23 eV, in line with the existing literature, as shown in Figure S7 of the Supporting Information.…”

Section: Resultssupporting

confidence: 89%

Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from Ab Initio Many-Body Theory

2020

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Lewis acids like tris(pentafluorophenyl)borane (BCF) offer promising routes for efficient p-doping of organic semiconductors. The intriguing experimental results achieved so far call for a deeper understanding of the underlying doping mechanisms. In a firstprinciples work, based on state-of-the-art density-functional theory and many-body perturbation theory, we investigate the electronic and optical properties of donor/acceptor complexes formed by quarterthiophene (4T) doped by BCF. For reference, hexafluorobenzene (C 6 F 6) and BF 3 are also investigated as dopants for 4T. Modelling the adducts as bimolecules in vacuo, we find negligible charge transfer in the ground state and frontier orbitals either segregated on opposite sides of the interface (4T:BCF) or localized on the donor (4T:BF 3 , 4T:C 6 F 6). In the optical spectrum of 4T:BCF, a charge-transfer excitation appears at lowest-energy, corresponding to the transition between the frontier states, which exhibit very small but non-vanishing wave-function overlap. In the other two adducts, the absorption is given by a superposition of the features of the constituents. Our results clarify that the intrinsic electronic interactions between donor and acceptor are not responsible for the doping mechanisms induced by BCF and related Lewis acids. Extrinsic factors, such as solvent-solute interactions, intermolecular couplings, and thermodynamic effects, have to be systematically analyzed for this purpose.

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Section: Resultssupporting

confidence: 89%

Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from Ab Initio Many-Body Theory

2020

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“…It is relevant to mention that our electron energy loss spectroscopy data at low electron impact energy and relatively high scattering angle enhances singlet to triplet transitions against the singlet to singlet transitions. Such spectroscopic evidence has been reported by us on previous occasions with other molecular targets with potential use in the plasma processing industry and fully supported by theoretical calculations. − Rydberg state spectroscopy has been performed with the help of available ionization energy values, although we have obtained vertical ionization energies (IEs) at different levels of theory, the results being presented in Table . A close comparison between the different methods in Table a shows that these agree reasonably well with each other with the exception of Koopmans’ theorem, ROHF and RMP2.…”

Section: Resultssupporting

confidence: 76%

Studies on GeF₄ Valence and Rydberg States by Electron Impact Spectroscopy and Ab Initio Calculations

et al. 2016

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Electron energy loss (EEL) spectra of GeF have been measured with incident electrons at 100 eV for 5° scattering angle and at 30 eV for 30° scattering angle, while sweeping the energy loss over the range 7.0-18.0 eV. Low-lying excited triplet, singlet, valence, and Rydberg states are investigated and the assignments supported by quantum chemical ab initio calculations. This provides the first comprehensive investigation of all singlet and triplet excited electronic states of germanium tetrafluoride up to the first ionization energy. The Rydberg series converging to the (lowest) ionization energy limits of GeF are also identified according to the magnitude of the quantum defects (δ).

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“…7(a) shows the inelastic ICSs for degenerate stretching, v 3 mode and composed (v 1 + v 2 + v 4 ) modes together with the total inelastic ICSs from the present IAM-SCAR calculations. BE f -scaled ICSs for the optically allowed transition of (π → π * ) at 13.13 eV were reported more recently 55 by our group and previous ionization cross sections 3,4,10 are also plotted in Fig. 7(a).…”

Section: E Integral and Momentum Transfer Cross Sections: Q I And Q Mmentioning

confidence: 59%

Crossed-beam experiment for the scattering of low- and intermediate-energy electrons from BF3: A comparative study with XF3 (X = C, N, and CH) molecules

Hoshino

Limão‐Vieira

Suga

et al. 2015

The Journal of Chemical Physics

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Absolute differential cross sections (DCSs) for electron interaction with BF 3 molecules have been measured in the impact energy range of 1.5-200 eV and recorded over a scattering angle range of 15 • -150 • . These angular distributions have been normalized by reference to the elastic DCSs of the He atom and integrated by employing a modified phase shift analysis procedure to generate integral cross sections (ICSs) and momentum transfer cross sections (MTCSs). The calculations of DCSs and ICSs have been carried out using an independent atom model under the screening corrected additivity rule (IAM-SCAR). The present elastic DCSs have been found to agree well with the results of IAM-SCAR calculation above 20 eV, and also with a recent Schwinger multichannel calculation below 30 eV. Furthermore, in the comparison with the XF 3 (X = B, C, N, and CH) molecules, the elastic DCSs reveal a similar angular distribution which are approximately equal in magnitude from 30 to 200 eV. This feature suggests that the elastic scattering is dominated virtually by the 3-outer fluorine atoms surrounding the XF 3 molecules. The vibrational DCSs have also been obtained in the energy range of 1.5-15 eV and vibrational analysis based on the angular correlation theory has been carried out to explain the nature of the shape resonances. Limited experiments on vibrational inelastic scattering confirmed the existence of a shape resonance with a peak at 3.8 eV, which is also observed in the vibrational ICS. Finally, the estimated elastic ICSs, MTCSs, as well as total cross sections are compared with the previous cross section data available. C 2015 AIP Publishing LLC. [http://dx

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BF₃ Valence and Rydberg States As Probed by Electron Energy Loss Spectroscopy and ab Initio Calculations

Cited by 6 publications

References 49 publications

Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from Ab Initio Many-Body Theory

Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from Ab Initio Many-Body Theory

Studies on GeF₄ Valence and Rydberg States by Electron Impact Spectroscopy and Ab Initio Calculations

Crossed-beam experiment for the scattering of low- and intermediate-energy electrons from BF3: A comparative study with XF3 (X = C, N, and CH) molecules

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BF3 Valence and Rydberg States As Probed by Electron Energy Loss Spectroscopy and ab Initio Calculations

Cited by 6 publications

References 49 publications

Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from Ab Initio Many-Body Theory

Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from Ab Initio Many-Body Theory

Studies on GeF4 Valence and Rydberg States by Electron Impact Spectroscopy and Ab Initio Calculations

Crossed-beam experiment for the scattering of low- and intermediate-energy electrons from BF3: A comparative study with XF3 (X = C, N, and CH) molecules

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BF₃ Valence and Rydberg States As Probed by Electron Energy Loss Spectroscopy and ab Initio Calculations

Studies on GeF₄ Valence and Rydberg States by Electron Impact Spectroscopy and Ab Initio Calculations