Electron affinities of cyano-substituted ethylenes

Brinkmann, Nicole R.; Rienstra-Kiracofe, Jonathan C.; Schaefer, Henry F.

doi:10.1080/00268970010028818

Cited by 15 publications

(9 citation statements)

References 69 publications

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“…[23][24][25][34][35][36] Regarding bond angles, the computed values and the experimental data are in agreement within one degree. The CÀCN segment is predicted to deviate slightly from linearity, in line with previous theoretical results [4,10,26,33] and with the conclusions obtained through X-ray and neutron diffraction measurements. [22,23,35] Addition of an electron to TCNE yields significant changes in the geometry (cf.…”

Section: Geometry and Electron Affinitysupporting

confidence: 89%

“…[21] Calculations were carried out within the constraints of D 2h symmetry, since planar structures for the neutral and radical monoanion TCNE have been well established both experimentally [22][23][24][25] and theoretically. [7,8,10,[26][27][28][29] Standard orientations were used for the molecular axes. For the computation of the vertical excitation energies the basis set was supplemented with a set of specifically designed 1s1p1d Rydberg-type functions contracted from a set of 8s8p8d primitives placed at the center of the molecule, according to the procedure explained elsewhere.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of the Electronic Excited States of Tetracyanoethylene and Its Radical Anion

et al. 2005

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The low-lying electronic states of tetracyanoethylene (TCNE) and its radical anion were studied using multiconfigurational second-order perturbation theory (CASPT2) and extended atomic natural orbital (ANO) basis sets. The results obtained yield a full interpretation of the electronic absorption spectra, explain the spectral changes undergone upon reduction, give support to the occurrence of a bound excited state for the anionic species, and provide valuable information for the rationalization of the experimental data obtained with electron transmission spectroscopy.

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Section: Geometry and Electron Affinitysupporting

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Electronic Excited States of Tetracyanoethylene and Its Radical Anion

et al. 2005

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“…34–36 Regarding bond angles, the computed values and the experimental data are in agreement within one degree. The CCN segment is predicted to deviate slightly from linearity, in line with previous theoretical results4, 10, 26, 33 and with the conclusions obtained through X‐ray and neutron diffraction measurements 22. 23, 35…”

Section: Resultssupporting

confidence: 89%

“…Calculations were carried out within the constraints of D 2 h symmetry, since planar structures for the neutral and radical monoanion TCNE have been well established both experimentally22–25 and theoretically 7. 8, 10, 26–29 Standard orientations were used for the molecular axes.…”

Section: Computational Detailsmentioning

confidence: 99%

Atomistic Modelling and Simulation of Warm Dense Matter. Conductivity and Reflectivity

Norman¹,

Saitov²,

Stegaĭlov³

et al. 2013

Contrib. Plasma Phys.

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Unfortunately in our recently published paper "Atomistic Modelling and Simulation of Warm Dense Matter. Conductivity and Reflectivity" we typeset inaccurately the equation (1) that manifests the essence of the method used for calculations. The following formula shows correctly the method used for calculation of the imaginary part of the dielectric function implemented in the VASP code:where q is the Bloch vector of the incident wave, vectors e a are the unit vectors for the three Cartesian directions. As shown in [M. Gajdos et al., Phys. Rev. B 73, 045112 (2006)] this formula takes into account the effects of microscopic field within the density functional theory in contrast to the Kubo-Greenwood formula presented in the published text. Besides, the expression "effects of the microscopic field in plasma" is more adequate than the phrase "local field effects" used in the published text. We are very grateful to Dr. M.P. Desjarlais for bringing this fact to our attention.These corrections do not affect any numerical results presented in the paper.

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“…5 Investigations using the density functional theory (DFT) with five different gradient-corrected functionals give a range of EA values from 1.35 to 2.13 eV, depending on the method used. 6 The triplet state of fumaronitrile was observed to lie 59 ± 2 kcal/mol (2.56 ± 0.09 eV) above the ground-state singlet, using the Herkstroeter−Hammond laser flash photolysis method. 7 The triplet energy surface has a minimum at a bisected geometry, with a depth ∼9 kcal/mol with respect to H−C−CN rotation, as determined from the M06-2X/6-311+G(2d,p) density-functional theory (DFT) calculations.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry of Fumaronitrile Radical Anion and Its Clusters

et al. 2014

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The photodetachment and photochemistry of the radical anion of fumaronitrile (trans-1,2-dicyanoethylene) and its clusters are investigated using photoelectron imaging and photofragment spectroscopy. We report the first direct spectroscopic determination of the adiabatic electron affinity (EA) of fumaronitrile (fn) in the gas phase, EA = 1.21 ± 0.02 eV. This is significantly smaller than one-half the EA of tetracyanoethylene (TCNE). The singlet-triplet splitting in fumaronitrile is determined to be ΔES-T ≤ 2.6 eV, consistent with the known properties. An autodetachment transition is observed at 392 and 355 nm and assigned to the (2)Bu anionic resonance in the vicinity of 3.3 eV. The results are in good agreement with the predictions of the CCSD(T) and EOM-XX-CCSD(dT) (XX = IP, EE) calculations. The H2O and Ar solvation energies of fn(-) are found to be similar to the corresponding values for the anion of TCNE. In contrast, a very large (0.94 eV) photodetachment band shift, relative to fn(-), is observed for (fn)2(-). In addition, while the photofragmentation of fn(-), fn(-)·Ar, and fn(-)(H2O)1,2 yielded only the CN(-) fragment ions, the dominant anionic photofragment of (fn)2(-) is the fn(-) monomer anion. The band shift, exceeding the combined effect of two water molecules, and the fragmentation pattern, inconsistent with an intact fn(-) chromophore, rule out an electrostatically solvated fn(-)·fn structure of (fn)2(-) and favor a covalently bound dimer anion. A C2 symmetry (fn)2(-) structure, involving a covalent bond between the two fn moieties, is proposed.

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Electron affinities of cyano-substituted ethylenes

Cited by 15 publications

References 69 publications

Theoretical Study of the Electronic Excited States of Tetracyanoethylene and Its Radical Anion

Theoretical Study of the Electronic Excited States of Tetracyanoethylene and Its Radical Anion

Atomistic Modelling and Simulation of Warm Dense Matter. Conductivity and Reflectivity

Photochemistry of Fumaronitrile Radical Anion and Its Clusters

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