The Dynamics of Unimolecular Reactions.

Kassel, Louis S.

doi:10.1021/cr60035a002

Cited by 18 publications

(6 citation statements)

References 9 publications

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“…In the most commonly used theories of this class, TST (30)(31)(32) and RRKM theory (33)(34)(35)(36), one begins by searching for a hypothetical dividing surface (DS) separating reactant(s) from product(s). The key feature of the DS is that reactive trajectories-those making their way from reactants to products-cross it only once.…”

Section: The Potential Energy Landscape and Reaction Rate Theorymentioning

confidence: 99%

Roaming: A Phase Space Perspective

Mauguière

Collins

Kramer

et al. 2017

Annu. Rev. Phys. Chem.

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In this review we discuss the recently described roaming mechanism for chemical reactions from the point of view of nonlinear dynamical systems in phase space. The recognition of the roaming phenomenon shows the need for further developments in our fundamental understanding of basic reaction dynamics, as is made clear by considering some questions that cut across most studies of roaming: Is the dynamics statistical? Can transition state theory be applied to estimate roaming reaction rates? What role do saddle points on the potential energy surface play in explaining the behavior of roaming trajectories? How do we construct a dividing surface that is appropriate for describing the transformation from reactants to products for roaming trajectories? How should we define the roaming region? We show that the phase space perspective on reaction dynamics provides the setting in which these questions can be properly framed and answered. We illustrate these ideas by considering photodissociation of formaldehyde. The phase-space formulation allows an unambiguous description of all possible reactive events, which also allows us to uncover the phase space mechanism that explains which trajectories roam, as opposed to evolving toward a different reactive event.

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Section: The Potential Energy Landscape and Reaction Rate Theorymentioning

confidence: 99%

Roaming: A Phase Space Perspective

Mauguière

Collins

Kramer

et al. 2017

Annu. Rev. Phys. Chem.

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show abstract

“…Frey (S) has recently reviewed the literature on the pyrolysis of hydrocarbons and the hypotheses relating to the mechanisms proposed to account for the reactions observed. The important mechanisms considered are those sponsored by Rice (IS), Burk (1), and Kassel (5).…”

Section: Interpretation Of Resultsmentioning

confidence: 99%

Pyrolysis of pronane in Presence of Water Vapor

lang¹,

Morgan²

1935

Ind. Eng. Chem.

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“…Numerous other suggestions have been made to explain how a molecule may split so as to give rise to several different products. Thus it has been suggested (85) that the decomposition of a paraffin might proceed by RCH2CH3 RH + CH3CH= CH3CH= -* CH2=CH2 i.e., an initial split to give an alkylidene radical which rearranges practically instantaneously to an olefin. In this case, if the second reaction were fast enough, the process would be indistinguishable from a direct split into stable molecules.…”

Section: Rimentioning

confidence: 99%

The Kinetics of Elementary Reactions of the Simple Hydrocarbons.

Steacie¹

1938

Chem. Rev.

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The Dynamics of Unimolecular Reactions.

Cited by 18 publications

References 9 publications

Roaming: A Phase Space Perspective

Roaming: A Phase Space Perspective

Pyrolysis of pronane in Presence of Water Vapor

The Kinetics of Elementary Reactions of the Simple Hydrocarbons.

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