The electron affinities of the perfluorocarbons C2Fn, n=1–6

King, Rollin A.; Pettigrew, Nathan D.; Schaefer, Henry F.

doi:10.1063/1.475005

Cited by 40 publications

(51 citation statements)

References 48 publications

(30 reference statements)

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“…Spectroscopic parameters such as the harmonic and anharmonic frequencies, rotational constant, and vibration–rotation constants have been obtained by combination of matrix and high‐resolution IR measurements with the MP2 calculations by Bürger et al 42 and later improved by Breidung et al 43 at the CCSD and CCSD(T) levels. Various DFT methods have been used for the evaluation of the structural parameters, electron affinity, and harmonic vibrational frequencies of C 2 F 2 44. The best results were obtained with the hybrid DFT methods, while the “pure” DFT methods (e.g., BLYP and BP86) incorrectly predict nonlinear equilibrium geometries for the ground state.…”

Section: Introductionmentioning

confidence: 99%

Oligopeptides as catalysts for asymmetric epoxidation

Kelly

Roberts

2005

Biopolymers

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Section: Introductionmentioning

confidence: 99%

Oligopeptides as catalysts for asymmetric epoxidation

Kelly

Roberts

2005

Biopolymers

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“…C 2 F 2 − corresponds to a HF loss from the PTR product. However, using the reported EA of C 2 F 2 , reaction Equation is found endothermic by 25 kJ.mol −1 .

{CF}_{3} {CH}_{3} + O^{-} \to C_{2} {normalF}_{2}^{-} + H_{2} normalO + HF .

…”

Section: Resultsmentioning

confidence: 96%

“…The latter ion is the most important product in the spectra. C 2 F 4 − may be due to the heterolytic fragmentation of the above mentioned intermediate [ − O─CH 2 ─CF • ─CF 3 ] leading to the formation of a formaldehyde neutral molecule and − CF─CF 3 that should isomerize to CF 2 ═CF 2 − as the interconversion is slightly in favor of the second structure according to King et al…”

Section: Resultsmentioning

confidence: 99%

“…− may be due to the heterolytic fragmentation of the above mentioned intermediate [ − O─CH 2 ─CF • ─CF 3 ] leading to the formation of a formaldehyde neutral molecule and − CF─CF 3 that shouldisomerize to CF 2 ═CF 2 − as the interconversion is slightly in favor of the second structure according to King et al84 Dawson and Jennings studying a less fluorinated molecule CF 3 CHCH 2 in an ICR apparatus observed 3 pathways as well 90. The main difference stands in the inversion of the branching ratios of the addition product and the H 2 + formal transfer product.…”

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confidence: 99%

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Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

et al. 2018

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The reactivity of a series of commonly used halogenated compounds (trihalomethanes, chlorofluorocarbon, hydrochlorofluorocarbon, fluorocarbons, and hydrofluoroolefin) with hydroxide and oxygen anion is studied in a compact Fourier transform ion cyclotron resonance. O is formed by dissociative electron attachment to N O and HO by a further ion-molecule reaction with ammonia. Kinetic experiments are performed by increasing duration of introduction of the studied molecule at a constant pressure. Hydroxide anion reactions mainly proceed by proton transfer for all the acidic compounds. However, nucleophilic substitution is observed for chlorinated and brominated compounds. For fluorinated compounds, a specific elimination of a neutral fluorinated alkene is observed in our results in parallel with the proton transfer reaction. Oxygen anion reacts rapidly and extensively with all compounds. Main reaction channels result from nucleophilic substitution, proton transfer, and formal H transfer. We highlight the importance of transfer processes (atom or ion) in the intermediate ion-neutral complex, explaining part of the observed reactivity and formed ions. In this paper, we present the first reactivity study of anions with HFO 1234yf. Finally, the potential of O and HO as chemical ionization reagents for trace analysis is discussed.

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“…With the large number of modest size molecules the inexpensive gradient corrected density functional methods (DFT) were considered adequate. DFT has been shown to be effective for predicting molecular structures for many related inorganic species, such as AsF n ,14 BrF n ,17 SF n ,18 PF n ,19 ClF n ,20 GeF n ,13 SeF n ,21 SiF n ,12 SiH n ,22 C 2 F n ,23 Si 2 F n ,15 and Ge 2 F n 16. Several different DFT methods are compared in the present study.…”

Section: Introductionmentioning

confidence: 99%

Structures and electron affinities of the di‐arsenic fluorides As₂F_n/As₂F (n = 1–8)

Kasalová

Schaefer

2005

J Comput Chem

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Developments in the preparation of new materials for microelectronics are focusing new attention on molecular systems incorporating several arsenic atoms. A systematic investigation of the As2Fn/As2Fn- systems was carried out using Density Functional Theory methods and a DZP++ quality basis set. Global and low-lying local geometric minima and relative energies are discussed and compared. The three types of neutral-anion separations reported in this work are: the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). Harmonic vibrational frequencies pertaining to the global minimum for each compound are reported. From the first four studied species (As2Fn, n=1-4), all neutral molecules and their anions are shown to be stable with respect to As-As bond breaking. The neutral As2F molecule and its anion are predicted to have Cs symmetry. We find the trans F-As-As-F isomer of C2h symmetry and a pyramidalized vinylidene-like As-As-F2- isomer of Cs symmetry to be the global minima for the As2F2 and As2F2- species, respectively. The lowest lying minima of As2F3 and As2F3- are vinyl radical-like structures F-As-As-F2 of Cs symmetry. The neutral As2F4 global minimum is a trans-bent (like Si2H4) F2-As-As-F2 isomer of C2 symmetry, while its anion is predicted to have an unusual fluorine-bridged (C(1)) structure. The global minima of the neutral As2Fn species, n=5-8, are weakly bound complexes, held together by dipole-dipole interactions. All such structures have the AsFm-AsFn form, where (m,n) is (2,3) for As2F5, (3,3) for As2F6, (4,3) for As2F7), and (5,3) for As2F8. For As2F8 the beautiful pentavalent F4As-AsF4 structure (analogous to the stable AsF5 molecule) lies about 30 kcal/mol above the AsF3 . . . AsF5 complex. The stability of AsF(5) depends crucially on the strong As-F bonds, and replacing one of these with an As-As bond (in F4As-AsF4) has a very negative impact on the molecule's stability. The anions As2Fn-, n=5-8, are shown to be stable with respect to the As-As bond breaking, and we predict that all of them have fluorine-bridged or fluorine-linked structures. The zero-point vibrational energy corrected adiabatic electron affinities are predicted to be 2.28 eV (As2F), 1.95 eV (As2F2), 2.39 eV (As2F3), 1.71 eV (As2F4), 2.72 eV (As2F5), 1.79 eV (As2F6), 5.26 eV (As2F7), and 3.40 eV (As2F8) from the BHLYP method. Vertical detachment energies are rather large, especially for species with fluorine-bridged global minima, having values up to 6.45 eV (As2F7, BHLYP).

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The electron affinities of the perfluorocarbons C2Fn, n=1–6

Abstract: Articles you may be interested inElectronic structures and chemical bonding in transition metal monosilicides M Si ( M = 3 d , 4 d , 5 d elements)

Cited by 40 publications

References 48 publications

Oligopeptides as catalysts for asymmetric epoxidation

Oligopeptides as catalysts for asymmetric epoxidation

Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

Structures and electron affinities of the di‐arsenic fluorides As₂F_n/As₂F (n = 1–8)

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The electron affinities of the perfluorocarbons C2Fn, n=1–6

Abstract: Articles you may be interested inElectronic structures and chemical bonding in transition metal monosilicides M Si ( M = 3 d , 4 d , 5 d elements)

Cited by 40 publications

References 48 publications

Oligopeptides as catalysts for asymmetric epoxidation

Oligopeptides as catalysts for asymmetric epoxidation

Oxygen anion (O−) and hydroxide anion (HO−) reactivity with a series of old and new refrigerants

Structures and electron affinities of the di‐arsenic fluorides As2Fn/As2F (n = 1–8)

Contact Info

Product

Resources

About

Oxygen anion (O⁻) and hydroxide anion (HO⁻) reactivity with a series of old and new refrigerants

Structures and electron affinities of the di‐arsenic fluorides As₂F_n/As₂F (n = 1–8)