Recent advances in flow tubes: Measurement of ion–molecule rate coefficients and product distributions

Smith, David; Adams, Nigel G.

doi:10.1016/b978-0-12-120801-1.50007-7

Cited by 14 publications

(10 citation statements)

References 115 publications

(92 reference statements)

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“…Thus one would expect that the three hydrogen atoms in the anion will exchange with either reagent. In fact, CH 3 OD does exchange all three, but D 2 O exchanges only one. This indicates that DO ῍ is trapped on one side of the benzene ring and cannot access the other side bearing two hydrogen atoms, whereas CH 3 O ῍ can migrate freely within the complex.…”

Section: ) 73)mentioning

confidence: 99%

“…Cl is found to be more than two orders of magnitude faster than the carbon-center analog of 37 Cl ῌ ῍ CH 3 35 Cl (Eq. (12)).…”

Section: ) 82)mentioning

confidence: 99%

“…As it turned out, the "simple" S N 2 reaction (Eq. (12) 3 Cl intramolecular mode, resulting in the failure to utilize the translational energy to surmount the central S N 2 barrier. 48) Orientational and angularmomentum constraints are also suggested to explain the ine$cient translational activation observed.…”

Section: )mentioning

confidence: 99%

“…4a), which must be dynamically restricted (see below). A more recent, ab initio direct dynamics trajectory simulation supports the back-side S N 2 mechanism 46) ; substantial vibrational excitation in the CH 3 Cl reactant is required to access the front-side transition state, and even so, the front-side pathway will still be dominated by the back-side reaction.…”

Section: )mentioning

confidence: 99%

“…Among the methyl chloride series, the CH 3 ClῌF ῌ reaction shows a nonstatistical behavior such that the rate is independent of the reactant internal energy. 54) A direct mechanism without formation of a long-lived complex has been suggested from the observed deviation of reaction cross sections at high collision energies 62) and by ab initio direct dynamics calculations (collision energy not specified).…”

Section: Fundamental Aspects Of Gas Phase Ion Chemistry Studied Usingmentioning

confidence: 99%

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Fundamental Aspects of Gas Phase Ion Chemistry Studied Using the Selected Ion Flow Tube Technique

Kato¹

2005

J. Mass Spectrom. Soc. Jpn.

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Gas phase ion chemistry using the selected ion flow tube (SIFT) technique is discussed with the focus on fundamental studies on ion structure, energetics, reactivity, and dynamics: Laser-induced fluorescence (LIF) kinetics/dynamics of N 2 ῍ (v) ions (vibrationally state-selected ion῎molecule reactions; energy transfer processes), mechanisms of prototypical organic ion reactions (S N 2 nucleophilic substitution and kinetic isotope e#ects; hydrogen/deuterium exchange; isotope e#ects in termolecular association), and ion῎molecule reactions with biological implications (S N 2 reactions at a nitrogen center; E CO 2 elimination reactions of alkyl hydroperoxides). Anion chemistry of small nitroalkanes is also presented. A powerful combination of SIFT and negative ion photoelectron spectroscopy is used to study thermochemistry and structure of energetic and exotic ions (alkyl peroxides; anionic derivatives of diazo and azole compounds, cyclooctatetraene, and cyclopentanone). Finally, some of the new directions in SIFT research are discussed, i.e., reactions of ions with polyatomic organic radicals, and chemical ionization mass spectrometry with new detection schemes.

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Section: ) 73)mentioning

confidence: 99%

“…Cl is found to be more than two orders of magnitude faster than the carbon-center analog of 37 Cl ῌ ῍ CH 3 35 Cl (Eq. (12)).…”

Section: ) 82)mentioning

confidence: 99%