A study of the electron-impact ionization of chlorine trifluoride and its decomposition products by mass spectrometry

Dudin, A. V.; Gorokhov, L. N.; Baluev, A. V.

doi:10.1007/bf00951688

Cited by 5 publications

(6 citation statements)

References 7 publications

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“…DeKock et al reported the lowest ionization energy of ClF 3 (X 1 A 1 ) to be 12.65 ± 0.05 eV and assigned the product as the 2 B 2 or 2 A 1 state of ClF 3 + . Irsa and Friedman and Dudin et al reported the IP to be around 13.0 eV. In contrast to experimental assignment noted above, our calculation found ground state ClF 3 + to have C s symmetry; like SF 3 , it is a 2 A′ state.…”

Section: Results and Discussion: States Of Clf N + Speciescontrasting

confidence: 94%

“…Dudin et al reported the appearance potential of ClF 2 + to be 12.77 ± 0.05 eV. Irsa and Friedman reported a very similar result, 12.8 ± 0.3 eV.…”

Section: Results and Discussion: States Of Clf N + Speciesmentioning

confidence: 88%

“… a Energies in hartrees ( E h ), bond lengths ( R e ) in Å, and bond angles (θ e ) in degrees. b Reference . c Reference . d Reference ; 1.551 Å is the average bond length reported in the paper. …”

Section: Results and Discussion: General Trendsmentioning

confidence: 99%

“…Based on the assumption that the energy levels of ClF should be similar to Cl 2 and F 2 , they assigned the energies for ionizing ClF to ClF + ( 2 Π) and ClF + ( 2 Σ + ) to be 16.39 ± 0.01 and 17.80 . Dudin et al 20 reported the appearance potential of ClF 2 + to be 12.77 ± 0.05 eV. Irsa and Friedman 17 reported a very similar result, 12.8 ± 0.3 eV.…”

Section: Ionization Energies (Ie)mentioning

confidence: 88%

“…A number of experimental studies − have been reported on ClF + and the closed shell species ClF 2 + , ClF 4 + , and ClF 6 + . For the open shell species, ClF 3 + and ClF 5 + , few experimental results are available due to the (chemical) instability of the species.…”

Section: Introductionmentioning

confidence: 99%

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High Level ab Initio Calculations for ClF_n⁺(n= 1–6) Ions: Refining the Recoupled Pair Bonding Model

Chen

Dunning

2013

J. Phys. Chem. A

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Based on detailed, high level ab initio calculations on a number of halogenated compounds of second row, late p-block elements, the SF(n), ClF(n), PFn, SCl(n), and SF(n)Cl families, we found that a new type of bond--the recoupled pair bond--accounts for the ability of these elements to form hypervalent, or hypercoordinated, compounds. Hypervalent molecules are formed when it is energetically favorable for the electrons in a lone pair orbital to be recoupled, allowing each of the electrons to form chemical bonds with ligands. In this paper, we characterize the structures and energies of the ground and low-lying excited states of the ClF(n)(+) (n = 1-6) ions, using high level ab initio methods [MRCI, CCSD(T)/RCCSD(T)] with large correlation consistent basis sets. We computed a number of quantities, including ClF(n)(+) structures, bond dissociation energies, and ClF(n) ionization energies and compared our results with the available experimental data. Both the bond dissociation energies and the ionization energies oscillate, variations that are readily explained using the recoupled pair bonding model. Comparisons are drawn between the ClF(n)(+) cations and their counterparts in the isoelectronic SF(n) series, which possess many similarities. We found two significant differences between the ClF(n)(+) and the SF(n) series: (i) the bond dissociation energies of ClF(n)(+) are much weaker than those of the corresponding SF(n) species, and (ii) there is no stable (3)A2 state in ClF2(+) corresponding to the stable state found in SF2. An examination of the Mulliken populations at the HF/AVTZ level for ClF(n)(+) and SF(n) species predicts that the F atom in the axial (recoupled pair bonding) position is more highly charged than the F atom in the equatorial (covalent bonding) position; there is also less charge transfer to the F atoms in ClF(n)(+) than in SF(n). The positive charge on Cl(+) makes it more difficult for an F atom to attract electrons from Cl(+) than from S and correspondingly less favorable to recouple the electrons in the lone pair orbitals in the ClF(n)(+) species.

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Section: Results and Discussion: States Of Clf N + Speciescontrasting

confidence: 94%

“…Dudin et al reported the appearance potential of ClF 2 + to be 12.77 ± 0.05 eV. Irsa and Friedman reported a very similar result, 12.8 ± 0.3 eV.…”

Section: Results and Discussion: States Of Clf N + Speciesmentioning

confidence: 88%

Section: Results and Discussion: General Trendsmentioning

confidence: 99%

Section: Ionization Energies (Ie)mentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

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High Level ab Initio Calculations for ClF_n⁺(n= 1–6) Ions: Refining the Recoupled Pair Bonding Model

Chen

Dunning

2013

J. Phys. Chem. A

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Electron Affinities of Atoms, Molecules, and Radicals

Christodoulides

McCorkle

Christophorou

1984

Electron–Molecule Interactions and Their Applications

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High level ab initio calculations on ClF n − ( n = 1–6): Recoupled pair bonding involving a closed-shell central ion

Chen

Dunning

2017

Computational and Theoretical Chemistry

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A study of the electron-impact ionization of chlorine trifluoride and its decomposition products by mass spectrometry

Cited by 5 publications

References 7 publications

High Level ab Initio Calculations for ClF_n⁺(n= 1–6) Ions: Refining the Recoupled Pair Bonding Model

High Level ab Initio Calculations for ClF_n⁺(n= 1–6) Ions: Refining the Recoupled Pair Bonding Model

Electron Affinities of Atoms, Molecules, and Radicals

High level ab initio calculations on ClF n − ( n = 1–6): Recoupled pair bonding involving a closed-shell central ion

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A study of the electron-impact ionization of chlorine trifluoride and its decomposition products by mass spectrometry

Cited by 5 publications

References 7 publications

High Level ab Initio Calculations for ClFn+(n= 1–6) Ions: Refining the Recoupled Pair Bonding Model

High Level ab Initio Calculations for ClFn+(n= 1–6) Ions: Refining the Recoupled Pair Bonding Model

Electron Affinities of Atoms, Molecules, and Radicals

High level ab initio calculations on ClF n − ( n = 1–6): Recoupled pair bonding involving a closed-shell central ion

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Product

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High Level ab Initio Calculations for ClF_n⁺(n= 1–6) Ions: Refining the Recoupled Pair Bonding Model

High Level ab Initio Calculations for ClF_n⁺(n= 1–6) Ions: Refining the Recoupled Pair Bonding Model