Radiolysis of liquid n-butane

Shida, Shôji; Fujisaki, Noboru; Hatano, Yoshihiko; Tanno, Kuniyasu

doi:10.1021/j100687a024

Cited by 10 publications

(7 citation statements)

References 7 publications

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“…As the path approaches the barrier and s diminishes to about 0.65, the 0-0 contraction ceases and the remainder of the path involves chiefly hydrogenic motion as the proton is transferred (step 11). A similar two-step reaction path has been observed in the proton transfer in formic acid dimer [22] and in C,H; [231.…”

Section: Table I Equilibrium (Eq) and Transition State (Ts) Geometriesupporting

confidence: 54%

Proton transfer in H5O2+ and H3O2? with an external restraining force

Kar

Scheiner

1995

Int. J. Quantum Chem.

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mA comparative study between proton transfer in H,OZ and H,O; has been carried out using the 6-31 + G** basis set at the MP level. An external harmonic force is imposed between the two terminal hydrogens (one on either end of the complex) to restrain the H bond lengths to a range where two minima exist in the potential energy surface, while providing the OH, and OH-groups appropriate flexibility to approach one another during the course of transfer. The H bond length in the anion is found to be longer and more linear than that in the cation. Geometries and orientations of the subunits play an important role in determining the H bond length and the nonlinearity of the bond. Similar trends are noted for both the ions as the spring stiffens: The barrier reaches its asymptotic maximum for intermolecular force constants larger than about 7 mdyn/& as do the equilibrium and transition-state values of R(O0). The energy barrier for the anion is higher than that of the cation. For both systems, the intrinsic reaction coordinate divides the transfer process into two consecutive steps: The approach of the two 0 atoms is followed by the actual motion of the proton. In fact, the hydrogen-bonded hydrogen moves upward, perpendicular to the line joining the 0 atoms, during the first step. The first steps account for about 30% of the energy required for proton transfer in the cation, whereas for the anion it is about 45%. 0

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Section: Table I Equilibrium (Eq) and Transition State (Ts) Geometriesupporting

confidence: 54%

Proton transfer in H5O2+ and H3O2? with an external restraining force

Kar

Scheiner

1995

Int. J. Quantum Chem.

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“…[22][23][24][25]. More recently, index two [26][27][28] and higher index 29 saddles have been studied (see also Refs. [30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone

Mauguière

Collins

Kramer

et al. 2016

The Journal of Chemical Physics

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We examine the phase space structures that govern reaction dynamics in the absence of critical points on the potential energy surface. We show that in the vicinity of hyperbolic invariant tori, it is possible to define phase space dividing surfaces that are analogous to the dividing surfaces governing transition from reactants to products near a critical point of the potential energy surface. We investigate the problem of capture of an atom by a diatomic molecule and show that a normally hyperbolic invariant manifold exists at large atom-diatom distances, away from any critical points on the potential. This normally hyperbolic invariant manifold is the anchor for the construction of a dividing surface in phase space, which defines the outer or loose transition state governing capture dynamics. We present an algorithm for sampling an approximate capture dividing surface, and apply our methods to the recombination of the ozone molecule. We treat both 2 and 3 degrees of freedom models with zero total angular momentum. We have located the normally hyperbolic invariant manifold from which the orbiting (outer) transition state is constructed. This forms the basis for our analysis of trajectories for ozone in general, but with particular emphasis on the roaming trajectories. C 2016 AIP Publishing LLC.[http://dx

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“…propane are summarized in Tables 1 and 2, and The traces of water were reported to interfere are shown in Fig. 1 from the radiolysis of pure perdeuterated hydrocarbons (propane, cyclohexane, n-heptane) contained substantial amounts of HD (7,10,13). Ion neutralization on vessel walls, covered with a layer of adsorbed water, as well as reactions of hydrocarbon ions with the traces of desorbed water, followed by neutralization of H,O' ions, were supposed to account for such a surprising result.…”

Section: Experimental (Cz) I\/lnterinlsmentioning

confidence: 99%

The effect of reactant purity on the radiolysis of gaseous ethane and propane

Gawlowski¹,

Niedzielski²,

Herman³

1977

Can. J. Chem.

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The yields of products formed in the recombination of free radicals in the radiolysis of gaseous ethane and propane have been determined. The yields of butane from ethane radiolysis, and of 2, 3-dimethylbutane from propane radiolysis were found to be much lower than those reported in the literature.The yields of these products increased markedly in the presence of the traces of water, either desorbed from the walls or introduced with insufficiently dried reagents. The details of experimental procedures warranting the total elimination of water are given.

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Radiolysis of liquid n-butane

Cited by 10 publications

References 7 publications

Proton transfer in H5O2+ and H3O2? with an external restraining force

Proton transfer in H5O2+ and H3O2? with an external restraining force

Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone

The effect of reactant purity on the radiolysis of gaseous ethane and propane

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