Photodetachment of FSi(OMe)4− and FGe(OMe)4− anions: an experimental and theoretical study of gas-phase hypervalent Si and Ge species

Xavier, Luciano A.; Morgon, Nelson H.; Menegon, Jair J.; Riveros, José M.

doi:10.1016/s1387-3806(02)00702-9

Cited by 12 publications

(4 citation statements)

References 48 publications

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“…In addition, the energy profile can contribute to better comprehension of the dissociation channels obtained by collisional activation and tandem mass spectrometry studies. − Research groups have been devoted to many works involving mass spectrometry in combination with computational chemistry. ,− Although the latter technique has been widely applied to gas-phase chemistry, topological analysis of the electron density by the atoms in molecules (AIM) method has been rarely used for elucidation of fragmentation mechanism. , Thus, application of parameters generated by AIM shall aid analysis of the results regarding the fragmentation mechanism.…”

Section: Introductionmentioning

confidence: 99%

“…Over the last decades, the development of gas-phase chemistry has been accelerated by two crucial factors: increased computational power and design of new mass spectrometry techniques. − These advances have also contributed to improving several chemistry areas . Gas-phase chemistry is interesting for mass spectrometry analysis because it allows comparison of the intensity of pattern ions and their fragments and aids understanding of the structure of various species observed in the mass spectra. − …”

Section: Introductionmentioning

confidence: 99%

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Application of the Atoms in Molecules Theory and Computational Chemistry in Mass Spectrometry Analysis of 1,4-Naphthoquinone Derivatives

Vessecchi

Lopes

et al. 2011

J. Phys. Chem. A

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Mass spectrometry analysis of 2-(acylamino)-1,4-naphthoquinone derivatives was carried out using electrospray ionization ion source in combination with tandem mass spectrometry. Protonated molecules were dissociated by application of the collision-induced dissociation (CID), and the protonation sites were suggested on the basis of the HOMO, molecular electrostatic potential map (MEP), proton affinity, and Fukui functions calculated by B3LYP/6-31+G(d,p). The main fragmentation mechanisms undergone by the protonated ions were elucidated on the basis of energy, geometry, and topology analysis of equilibrium geometries. Compounds exhibiting only aliphatic hydrogens at the lateral chain undergo interesting ketene elimination. On the other hand, only the benzoylium ion formation is detected for 2-benzoylamino-1,4-naphthoquinone. The bonds geometric and atoms in molecules parameters give evidence that acidic hydrogen atoms play an important role in the fragmentation pathways.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Application of the Atoms in Molecules Theory and Computational Chemistry in Mass Spectrometry Analysis of 1,4-Naphthoquinone Derivatives

Vessecchi

Lopes

et al. 2011

J. Phys. Chem. A

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“…No processo de geração das bases, após a contração e representação dos elétrons internos pelo ECP, os parâmetros de discretização que descrevem as funções que representam os elétrons de valência (sem a adição das difusas) são reotimizados, originando os conjuntos de funções de base a serem usados. O MCG permite correção do caráter difuso de maneira racional 51 . Pela extrapolação da reta resultante da forma logarítmica, apresentada na Equação 4, obtém-se o valor do α da função difusa.…”

Section: Método Da Coordenada Geradora (Mcg)unclassified

Cálculos teóricos de afinidades por próton de n-alquilaminas usando o método ONIOM

Braga¹,

Morgon²

2006

Quím. Nova

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“…Dissociative photodetachment has also been used to probe the potential energy surfaces for the reaction of OH ϩ CO. 138 Riveros and co-workers have examined the structure of hypervalent silicon and germanium anions by using photodetachment. 139 Photodetachment of FX(OMe) 4 Ϫ (X = Si, Ge) required more than 3.5 eV. Although neutral photodetachment products were not detected, the experimental results indicated that the products are likely dissociated, involving loss of methoxyl radical [eqn.…”

Section: A Negative Ion Studiesmentioning

confidence: 99%

12 Organic gas-phase ion chemistry

Munsch

Wenthold

2003

Annu. Rep. Prog. Chem., Sect. B

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Gas-phase ion chemistry is a useful approach for the investigation of physical organic chemistry and the study of reactivity, structure, and thermochemical properties of ionic and neutral organic substrates. This review summarizes the physical organic chemistry studies utilizing gas-phase ion chemistry reported in the past year. Among the more significant advances reported in the past year included a report of the reactivity of p-benzyne by Kenttämaa and co-workers, 1 a comparison of the S N 2 reaction in the gas-phase and in solution by Brauman and co-workers, 2 and a full characterization of the structure and energetics of cyanocarbene. 3,4 Information learned from these gas-phase ion studies includes: 1) p-benzyne undergoes radical reactions but also reacts as a weak electrophile; 2) unlike what is found in solution, steric bulk does not significantly affect the barriers for S N 2 reactions of halogenated nitriles; and 3) HCCN is a "floppy" molecule with a triplet ground state and a singlet excited state that is ca. 50 kJ mol Ϫ1 higher in energy.Papers included in this review were selected by considering contributions to the standard organic, physical, and mass spectrometry journals. The selected articles are those that address the issue of reactivity and structure of organic molecules. Our emphasis in this work is on the chemistry that is observed, and information regarding the instrumental technique is only provided in situations where it is critical for understanding the results. The majority of the studies were carried out by using Fourier transform-ion cyclotron resonance (FT-ICR), quadrupole ion trap, or flowing afterglow techniques. We have generally not included papers regarding ionization fragmentation patterns, unless the work was part of broader studies. Studies of organometallic ions were generally not included if the chemistry was dominated by the metal center. Moreover, computational studies were also not included unless they provided significant insight into specific experimental results.It was with some trepidation that we restrict the number of biological studies included in this paper. Recent advances in mass spectrometric capabilities have led to numerous fundamental studies of the properties of biologically relevant molecules. In this work, we generally have only included the studies of the simplest biological molecules, amino acids, nucleic acids, and monosaccharides. It is clear that many more future mass spectrometric studies will likely involve biological substrates. As such, it is anticipated that future versions of this report may need to be expanded to include more biologically relevant material.The articles summarized in this review are organized into broad classifications: 420

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Photodetachment of FSi(OMe)4− and FGe(OMe)4− anions: an experimental and theoretical study of gas-phase hypervalent Si and Ge species

Cited by 12 publications

References 48 publications

Application of the Atoms in Molecules Theory and Computational Chemistry in Mass Spectrometry Analysis of 1,4-Naphthoquinone Derivatives

Application of the Atoms in Molecules Theory and Computational Chemistry in Mass Spectrometry Analysis of 1,4-Naphthoquinone Derivatives

Cálculos teóricos de afinidades por próton de n-alquilaminas usando o método ONIOM

12 Organic gas-phase ion chemistry

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