Rate of the Gaseous Reactions, X++YH=XH++Y

Stevenson, D. P.; Schissler, D. O.

doi:10.1063/1.1742283

Cited by 191 publications

(88 citation statements)

References 3 publications

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“…11,12 The C 4v and D 3h structures were predicted to be higher in energy than the e-C s structure by 1 kcal/mol and 9 kcal/mol, respectively. As pointed out by Schleyer, Schaefer, and later, by Scuceria, 13 the early prediction that CH 5 ϩ is regarded as a complex between CH 3 ϩ and H 2 with a localized 3c2e bond is not valid, but CH 5 ϩ is likely to scramble constantly through the low lying s-C s and C 2v transition states, without possessing a definite equilibrium structure.…”

Section: Chmentioning

confidence: 99%

“…3 Olah and co-workers later reported that CH 5 ϩ played an important role as a reactive intermediate in super acid solution reactions. 4 …”

Section: Chmentioning

confidence: 99%

Section: Chmentioning

confidence: 99%

“…5 It is also of astrophysical interest in that it may play as an intermediate for generation of methane and formaldehyde in the cold galactic molecular clouds. 6 A number of the early theoretical calculations on the structures of CH 5 ϩ consistently suggested that the eclipsed C s (e-C s ) symmetry structure was the global minimum energy structure. [7][8][9][10] However, recent ab initio calculations at the most sophisticated level, performed by Schleyer and coworkers, found that the energy differences between the e-C s structure and other structures such as staggered C s (s-C s ) or C 2v were very small and became negligible when corrected for zero point energies ͑see Fig.…”

Section: Chmentioning

confidence: 99%

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Infrared spectroscopy of the molecular hydrogen solvated carbonium ions, CH+5(H2)n (n=1–6)

Boo

Lee

1995

The Journal of Chemical Physics

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The infrared spectra for the molecular hydrogen-solvated carbonium ions, CH 5 ϩ ͑H 2 ͒ n (nϭ1 -6) in the frequency range of 2700-4200 cm Ϫ1 are presented. Spectroscopic evidence was found in support of the scrambling of CH 5 ϩ through the large amplitude motions such as the CH 3 internal rotation and the in-plane wagging motion of three-center two-electron bond. More importantly, the scrambling motions of CH 5 ϩ cores were slowed down considerably by attaching the solvent H 2 molecules to the core ion. The complete freezing of the scrambling motions was found when the first three H 2 molecules were bound to the CH 5 ϩ core. A good agreement between the experimental and the theoretical predictions was found in the dynamics of CH 5 ϩ .

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Section: Chmentioning

confidence: 99%

“…3 Olah and co-workers later reported that CH 5 ϩ played an important role as a reactive intermediate in super acid solution reactions. 4 …”

Section: Chmentioning

confidence: 99%

Section: Chmentioning

confidence: 99%

Section: Chmentioning

confidence: 99%

See 2 more Smart Citations

Infrared spectroscopy of the molecular hydrogen solvated carbonium ions, CH+5(H2)n (n=1–6)

Boo

Lee

1995

The Journal of Chemical Physics

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“…While ion-molecule reactions (IMRs) have a long history in MS, dating back to Sir J. J. Thomson's observation of H 3 + [8], prior to the 1950s IMRs were regarded as both a curiosity and a nuisance and were known to occur when ion sources were operated at higher pressures. It was the fundamental studies of gas-phase IMRs by Tal'roze and Lyubimova [9], Stevenson and Schissler [10], and Field et al [11] in the 1950s that laid the foundation of CIMS. As noted in Munson's accounts [3,4] [6].…”

mentioning

confidence: 99%

Chemical Ionization Mass Spectrometry: 50 Years on

O’Hair

2016

J. Am. Soc. Mass Spectrom.

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A quantum electronic theory of chemical processes?The inverted energy profile case: CH3+ + H2 reaction

Tapia¹,

Moliner²,

Andrés³

1997

Int. J. Quant. Chem.

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A quantum approach to chemical processes is developed. The chemical interconversion is described as an electronic process. The reaction corresponds to histories involving quantum states belonging to different stationary molecular Hamiltonians. The system Ž . may be embedded in a weak thermal andror external electromagnetic field. The electromagnetic transverse fields lead to transition moments yielding finite probability amplitudes for the system to change from one quantum state to another. Bottleneck Ž . subspaces transition states are defined; they mediate the interconversions in generic unimolecular and bimolecular processes. Active precursor and successor complexes are introduced to help bridge reactant and product electronic states. The stationary states are modeled with Born᎐Oppenheimer Hamiltonians. At a qualitative level, the theory is general. The rate, measured as a time derivative of product concentration, is expressed in terms of concentrations of active precursor and successor complexes. The kinetic coefficients are given in terms of quantum processes involving electronic bottleneck states. Stationary structures and vibrational zero-point energies characterizing the reactive CH qqH system are determined at a Hartree᎐Fock level of theory with 6-31qqGbasis set. The vibrational levels are corrected with anharmonicity effects. The saddle point of index one for hydrogen scrambling reactions has been obtained and shown to be related to the CH q molecular complex together with the precursor and successor 5 complexes geometries. The unusual properties of the system with respect to standard transition-state theory are fairly well described within this approach, in particular, isotope scrambling as well as photon emission during formation of the carbocation. The theory suggests that these types of reactions, which are found in outer space, may contribute to the scattering of the cosmic microwave background.

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Rate of the Gaseous Reactions, X++YH=XH++Y

Cited by 191 publications

References 3 publications

Infrared spectroscopy of the molecular hydrogen solvated carbonium ions, CH+5(H2)n (n=1–6)

Infrared spectroscopy of the molecular hydrogen solvated carbonium ions, CH+5(H2)n (n=1–6)

Chemical Ionization Mass Spectrometry: 50 Years on

A quantum electronic theory of chemical processes?The inverted energy profile case: CH3+ + H2 reaction

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