Attempts to calculate the electron affinity of acrylonitrile

Maloteau, M.; Mosley, David H.; André, Jean‐Marie; Delhalle, Joseph; Pickup, Barry T.

doi:10.1002/qua.560440851

Cited by 4 publications

(6 citation statements)

References 26 publications

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“…In Table , we have listed the target properties of acrylonitrile calculated using the HF level of theory in Quantemol-N and compared them with those properties obtained using DFT/B3LYP using GAMESS (US). The ground-state energy of −169.83 Hartree obtained through the HF level of theory in Quantemol-N is in agreement with the value of −170.80 Hartree obtained using the DFT/B3LYP/aug-cc-pVTZ level in GAMESS as well as with available theoretical data. , The present ionization energies are calculated using Koopman’s theorem in Quantemol-N and the DFT method (by taking the difference of the calculated neutral ground state and cationic ground state energies) in GAMESS. The values obtained using both the methods agree well with the available theoretical − as well as experimental data. ,, The optimized geometry is further used to compute the dipole moment which is the expectation value of charge multiplied by the distance in the optimized ground state.…”

Section: Theoretical Methodologysupporting

confidence: 84%

“… a Polarizability using 6-311G. b Polarizability using cc-pVTZ. c Polarizability using the 6-311G+(2d,2p) basis set. d Gutsev and Adamowicz e Maloteau et al f Polarizability using the NIST database g Watanabe et al h Bieri et al i Gluch et al j Ohno et al k Houk et al l Alía et al m Desfrançois et al n Suess et al o Nelson et al p CRC Handbook …”

Section: Theoretical Methodologymentioning

confidence: 99%

“…The ground-state energy of −169.83 Hartree obtained through the HF level of theory in Quantemol-N is in agreement with the value of −170.80 Hartree obtained using the DFT/ B3LYP/aug-cc-pVTZ level in GAMESS as well as with available theoretical data. 25,60 The present ionization energies are calculated using Koopman's theorem in Quantemol-N and the DFT method (by taking the difference of the calculated neutral ground state and cationic ground state energies) in GAMESS. The values obtained using both the methods agree well with the available theoretical 61−63 as well as experimental data.…”

Section: Approximations Used In the Presentmentioning

confidence: 99%

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Electronic Excitations and Low-Energy Electron-Induced Scattering Studies of Acrylonitrile (CH₂CHCN)

Vadhel¹,

Jani²,

Shastri

et al. 2022

J. Phys. Chem. A

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We report here theoretical investigations on structural, spectroscopic, and electron scattering for acrylonitrile (CH2CHCN), a molecule of importance in astrochemistry as well as the chemical industry. Quantum chemical calculations for ground and excited states are performed using density functional theory (DFT) and time-dependent-DFT methods, respectively. The results of geometry optimization and vibrational frequencies agree well with data available in the literature, while vertical excited singlet-state energies are extended to higher excited states as compared to earlier studies, including Rydberg and valence excitations. Quantum defect analysis and comparison of the theoretically predicted energies with earlier reported experimental works led to the confirmation of some spectral assignments and the revision of a few assignments. Vibrational frequencies calculated for the cationic ground state are used to tentatively assign vibrational bands appearing along with the Rydberg transitions. Triplet excited-state energies for which no data is available in the literature are reported here for the first time. Low-energy (0.1 to 20 eV) electron scattering calculations are performed using the ab initio R-matrix method. Several types of resonances are predicted in the energy-dependent elastic cross-section, most of which are in good agreement with earlier experimental or theoretical works, while a few new resonances are found above 6 eV. Additionally, calculations of eigenphase sum, differential, momentum transfer, electronic excitation, ionization, and total cross-sections are being reported for the first time. This work represents a comprehensive theoretical study of the electronically excited states as well as low-energy electron scattering of acrylonitrile, which would be useful for understanding its chemistry in the interstellar medium as well as industrial applications.

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Section: Theoretical Methodologysupporting

confidence: 84%

Section: Theoretical Methodologymentioning

confidence: 99%

Section: Approximations Used In the Presentmentioning

confidence: 99%

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Electronic Excitations and Low-Energy Electron-Induced Scattering Studies of Acrylonitrile (CH₂CHCN)

Vadhel¹,

Jani²,

Shastri

et al. 2022

J. Phys. Chem. A

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“…Prediction of electron affinities is a complex problem. Specifically, for AN, even high-level Hartree-Fock and MP2 calculations with augmented Gaussian basis sets 24 fail to obtain a bound state for the radical anion ͑which we take as a positive sign for EA͒, contrary to a small but positive experimental estimate of 0.01-0.02 eV, as well as to a general theorem 25,26 predicting the existence of stable anions for molecules having dipole moments larger than a certain critical value of 1.625 D; we note that experimentally the dipole moment of AN is 3.69 D. 27 The DNP TABLE I. Geometrical parameters of acrylonitrile neutral molecule and radical anion. The labels are those defined in Fig.…”

Section: A Acrylonitrile and Copper Clusters 1 Acrylonitrile Neutramentioning

confidence: 99%

Acrylonitrile on Cu(100): A density functional theoretical study of adsorption and electrochemical grafting

Geskin

Lazzaroni

Mertens

et al. 1996

The Journal of Chemical Physics

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We present a density functional theoretical study of neutral and negatively charged complexes of acrylonitrile (AN) with several clusters representing the Cu(100) surface. An external electric field is used to induce electron transfer onto the adsorbed molecule, in order to model the initial stage of electrochemical polymerization of AN on a copper electrode. We compare different possibilities of AN interaction with the metal and determine the most favorable configurations of the adsorbates in the absence and in the presence of the electric field. We discuss the influence of the electrochemical polarization on the type of AN adsorption, in relation with the experimental data on the adsorption of AN and electrochemical grafting of polyacrylonitrile.

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“…Due to its negative electron affinity, the mechanism leading to C 2 H 3 CN − desorption is challenging. It is known that isolated acrylonitrile does not lead to stable anions (Maloteau et al 1992). However, because of its high dipole moment (µ = 3.87 D), acrylonitrile can form a dipole-bound negative ion, whose measured binding energy is 6.505 meV (Suess et al 2003).…”

Section: Desorption Of Negative Ionsmentioning

confidence: 99%

Low-temperature chemistry induced by cosmic rays: positive and negative ion desorption from nitrile-bearing astrophysical ice analogues

Ribeiro

Almeida

Wolff

et al. 2019

Monthly Notices of the Royal Astronomical Society

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In cold core of dark molecular clouds, where the UV radiation from external sources is strongly attenuated, cosmic rays can induce chemical reactions on the surface of icecovered grains promoting the ejection of the processed material to the gas phase. We report the positive and negative secondary ion emission from pure CH 3 CN, C 2 H 3 CN and i−C 3 H 7 CN ices due to the bombardment of heavy ions ( 252 Cf fission fragments), simulating the incidence of cosmic rays onto icy surfaces. The secondary ions emitted from each sample were analysed by time-of-flight mass spectrometry (TOF-MS), using Plasma Desorption Mass Spectrometry (PDMS) technique. Several ionic species were identified, indicating strong fragmentation on the frozen surface. Proton-transfer processes are suggested to play a role for positive ion desorption, as evidenced by the protonated RCNH + parent molecules and (RCN) n H + ionic clusters. The high electron affinity of the cyano radical seems to contribute to the strong emission of CN − , as well as anions attributed to the CH m CN − fragment and (RCN) n CN − cluster series. Sputtering and desorption of ion clusters (positive and negative) induced by heavy ion bombardment are suggested to constitute a route by which new neutral or ionised molecular species may be delivered to the gas phase where thermal desorption is negligible.

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Attempts to calculate the electron affinity of acrylonitrile

Cited by 4 publications

References 26 publications

Electronic Excitations and Low-Energy Electron-Induced Scattering Studies of Acrylonitrile (CH₂CHCN)

Electronic Excitations and Low-Energy Electron-Induced Scattering Studies of Acrylonitrile (CH₂CHCN)

Acrylonitrile on Cu(100): A density functional theoretical study of adsorption and electrochemical grafting

Low-temperature chemistry induced by cosmic rays: positive and negative ion desorption from nitrile-bearing astrophysical ice analogues

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Attempts to calculate the electron affinity of acrylonitrile

Cited by 4 publications

References 26 publications

Electronic Excitations and Low-Energy Electron-Induced Scattering Studies of Acrylonitrile (CH2CHCN)

Electronic Excitations and Low-Energy Electron-Induced Scattering Studies of Acrylonitrile (CH2CHCN)

Acrylonitrile on Cu(100): A density functional theoretical study of adsorption and electrochemical grafting

Low-temperature chemistry induced by cosmic rays: positive and negative ion desorption from nitrile-bearing astrophysical ice analogues

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Product

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Electronic Excitations and Low-Energy Electron-Induced Scattering Studies of Acrylonitrile (CH₂CHCN)

Electronic Excitations and Low-Energy Electron-Induced Scattering Studies of Acrylonitrile (CH₂CHCN)