The formation of boron containing fragment ions from the ionization of BCl3

Love, Natalie A.; Price, S. D.

doi:10.1016/j.ijms.2003.12.019

Cited by 5 publications

(14 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2 ), although only 16 counts are recorded for this last pair, compared with 1300 for the most abundant pair. The experimental results show that there is no dissociation of BCl 3 to form BCl 2 , 13 and so the dication BCl 2þ 2 must come from the fragmentation of the parent dication BCl 2þ 3 , by the loss of a chlorine atom 13 (see Fig. 1, pathway A1).…”

Section: Experimental Observations Of the Decay Of Bcl 2þmentioning

confidence: 99%

“…We now present a brief summary of the experimental data obtained by Love and Price using time of flight mass spectroscopy (TOFMS) and ion-ion coincidence techniques. 13 The most abundant ion observed following the electron impact ionisation of BCl 3 is BCl þ 2 , the parent ion BCl…”

Section: Experimental Observations Of the Decay Of Bcl 2þmentioning

confidence: 99%

“…By contrast, the (B 1 þ Cl 1 ) ion pair results from a mechanism involving the initial fragmentation of BCl 2þ 3 by charge separation, followed by the subsequent fragmentation of these products. 13 It is suggested that the (BCl…”

Section: Experimental Observations Of the Decay Of Bcl 2þmentioning

confidence: 99%

“…2 ) ion pair is the intermediate in this process, since the calculated gradient (the ratio of the momenta of the separating species) for the products of pathway C2 is in good agreement with that observed. 13 Pathway C2 should also result in two unobservable chlorine atoms. It proved to be impossible to measure the gradient for the (Cl 1 þ Cl 1 ) ion pair, 13 and hence it is not known whether pathway D1 is single or multi-step, or which neutral species are produced.…”

Section: Experimental Observations Of the Decay Of Bcl 2þmentioning

confidence: 99%

“…The data obtained are used to augment experimental studies previously carried out in this department. 13…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

An ab initio study of the electronic structure of BCl2+3 and its decomposition pathways

Thomas

Kaltsoyannis

2006

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Ab initio methods have been used to characterise the lowest energy potential energy surfaces of 1BCl3(2+) and 3BCl3(2+). The methods used are MP2, CCSD, CCSD(T) and MCSCF with 6-311G(d), cc-pVTZ and aug-cc-pVTZ basis sets. While the singlet surface is relatively straight-forward, the triplet surface is very complicated, with many stationary points in close energetic proximity. The singlet surface can fragment to the following products (1BCl + 1Cl+ + 1Cl+), (1Cl+ + 1B+ + 1Cl2), (2BCl+ + 2Cl), while the triplet surface can fragment to (1BCl2+ + 3Cl+) and (2BCl2(2+) + 2Cl). 2BCl2(2+) can further fragment to (1Cl+ + 2BCl+). These results are in good agreement with previous experimental data from coincidence mass spectroscopy. [symbol: see text]1 diagnostic values have been calculated for all of the stationary points of BCl3(2+), using the method of Lee and Taylor. These data, together with CCSD/CCSD(T) energy differences and MCSCF calculations, are used to conclude that most of the stationary points on the singlet surface are well represented using single reference methods. The stationary points of the triplet system have [symbol: see text]1 diagnostic values greater than those for the singlet system, as expected when using the closed-shell [symbol: see text]1 diagnostic method of Lee and Taylor. However, all of the structures have acceptable single reference wavefunctions if the open-shell upper limit of Rienstra-Kiracofe et al. (0.045) is used, a conclusion fully supported by CCSD/CCSD(T) energy differences. CCSD(T) energies determined for the fragmentation asymptotes have been compared with experimental data collated from the NIST Theoretical and Scientific Data website, and the generally very good agreement between theory and experiment reinforces the reliability of the CCSD(T) method.

show abstract

Section: Experimental Observations Of the Decay Of Bcl 2þmentioning

confidence: 99%

Section: Experimental Observations Of the Decay Of Bcl 2þmentioning

confidence: 99%

Section: Experimental Observations Of the Decay Of Bcl 2þmentioning

confidence: 99%

Section: Experimental Observations Of the Decay Of Bcl 2þmentioning

confidence: 99%

“…The data obtained are used to augment experimental studies previously carried out in this department. 13…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

An ab initio study of the electronic structure of BCl2+3 and its decomposition pathways

Thomas

Kaltsoyannis

2006

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

Current literature in mass spectrometry

2005

J. Mass Spectrom.

View full text Add to dashboard Cite

In order to keep subscribers up-to-date with the latest developments in their field, John Wiley & Sons are providing a current awareness service in each issue of the journal. The bibliography contains newly published material in the field of mass spectrometry. Each bibliography is divided into 11 sections: 1 Books, Reviews & Symposia; 2 Instrumental Techniques & Methods; 3 Gas Phase Ion Chemistry; 4 Biology/Biochemistry: Amino Acids, Peptides & Proteins; Carbohydrates; Lipids; Nucleic Acids; 5 Pharmacology/Toxicology; 6 Natural Products; 7 Analysis of Organic Compounds; 8 Analysis of Inorganics/Organometallics; 9 Surface Analysis; 10 Environmental Analysis; 11 Elemental Analysis. Within each section, articles are listed in alphabetical order with respect to author (4 Weeks journals - Search completed at 12th. Jan. 2005).

show abstract

Electron ionization of acetylene

King

Price

2007

The Journal of Chemical Physics

View full text Add to dashboard Cite

Relative partial ionization cross sections and precursor specific relative partial ionization cross sections for fragment ions formed by electron ionization of C2H2 have been measured using time-of-flight mass spectrometry coupled with a 2D ion-ion coincidence technique. We report data for the formation of H+, H+2, C2+, C+/C2+ 2, CH+/C2H+2, CH+2, C+2, and C2H+ relative to the formation of C2H+2, as a function of ionizing electron energy from 30-200 eV. While excellent agreement is found between our data and one set of previously published absolute partial ionization cross sections, some discrepancies exist between the results presented here and two other recent determinations of these absolute partial ionization cross sections. We attribute these differences to the loss of some translationally energetic fragment ions in these earlier studies. Our relative precursor-specific partial ionization cross sections enable us, for the first time, to quantify the contribution to the yield of each fragment ion from single, double, and triple ionization. Analysis shows that at 50 eV double ionization contributes 2% to the total ion yield, increasing to over 10% at an ionizing energy of 100 eV. From our ion-ion coincidence data, we have derived branching ratios for charge separating dissociations of the acetylene dication. Comparison of our data to recent ab initio/RRKM calculations suggest that close to the double ionization potential C2H2+2 dissociates predominantly on the ground triplet potential energy surface (3Sigma*g) with a much smaller contribution from dissociation via the lowest singlet potential energy surface (1Delta g). Measurements of the kinetic energy released in the fragmentation reactions of C2H2+2 have been used to obtain precursor state energies for the formation of product ion pairs, and are shown to be in good agreement with available experimental data and with theory.

show abstract

The formation of boron containing fragment ions from the ionization of BCl3

Cited by 5 publications

References 39 publications

An ab initio study of the electronic structure of BCl2+3 and its decomposition pathways

An ab initio study of the electronic structure of BCl2+3 and its decomposition pathways

Current literature in mass spectrometry

Electron ionization of acetylene

Contact Info

Product

Resources

About