Dynamics-Driven Reaction Pathway in an Intramolecular Rearrangement

Ammal, Salai Cheettu; Yamataka, Hiroshi; Aida, Misako; Dupuis, Michel

doi:10.1126/science.1079491

Cited by 152 publications

(128 citation statements)

References 10 publications

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“…The 3 P states of oxygen have asymptotic degeneracies ͑5,3,1͒ corresponding to values of the total angular momentum ͑2,1,0͒, respectively. At short range these states correlate to 3 AЉ, 3 AЉ, and 3 AЈ surfaces. According to the treatment of Hoffmann and Schatz, only three of these nine are included in the four state model as only three have significant spin-orbit couplings with the one singlet state, and also correlate to ground-state products.…”

Section: A Implementationmentioning

confidence: 99%

“…[1][2][3] Quantum tunneling becomes negligible for heavy nuclei and quantum interference is often quenched in large molecular systems at short times due to the wave-function decoherence, but nonadiabatic effects can still influence such systems. The most widely used method for including nonadiabatic effects into the dynamics of molecules is the trajectory surface hopping method ͑TSH͒, 4,5 which is based on classical evolution of trajectories that can switch between different electronic states.…”

Section: Introductionmentioning

confidence: 99%

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Semiclassical nonadiabatic dynamics based on quantum trajectories for the O(P3,D1)+H2 system

Garashchuk

Rassolov

Schatz

2006

The Journal of Chemical Physics

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The O͑ 3 P , 1 D͒ +H 2 → OH + H reaction is studied using trajectory dynamics within the approximate quantum potential approach. Calculations of the wave-packet reaction probabilities are performed for four coupled electronic states for total angular momentum J = 0 using a mixed coordinate/polar representation of the wave function. Semiclassical dynamics is based on a single set of trajectories evolving on an effective potential-energy surface and in the presence of the approximate quantum potential. Population functions associated with each trajectory are computed for each electronic state. The effective surface is a linear combination of the electronic states with the contributions of individual components defined by their time-dependent average populations. The wave-packet reaction probabilities are in good agreement with the quantum-mechanical results. Intersystem crossing is found to have negligible effect on reaction probabilities summed over final electronic states.

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Section: A Implementationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Semiclassical nonadiabatic dynamics based on quantum trajectories for the O(P3,D1)+H2 system

Garashchuk

Rassolov

Schatz

2006

The Journal of Chemical Physics

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“…Since then, dynamics effects have been claimed to play an important role in various reactions. It appears in different ways, such as nonstatistical barrier recrossing, 3 nonstatistical product distribution, 4 shallow minimum skip on the intrinsic reaction coordinate (IRC), 5 non-IRC path, [6][7][8] and path bifurcation. 9,10 All these results suggested that the mechanism of these reactions could not be defined by the reaction paths on the PES and by the traditional TS theory.…”

Section: Introductionmentioning

confidence: 99%

Dynamic path bifurcation for the Beckmann reaction: observation and implication

et al. 2010

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The reaction of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles instead of amides when the cations have reasonable stability. The reactions of oxime derivatives of 1-substituted-phenyl-2-propanones and 3-substituted-phenyl-2-butanones in aqueous solvents gave both rearrangement and fragmentation products, the ratio of which was dependent on substituents. Transition state (TS) optimizations and intrinsic reaction coordinate (IRC) calculations for the reaction of 1-phenyl-2-propanone oximes showed that there is a single TS for each substituted compound. The IRC path from the TS either led to a rearrangement product or a fragmentation product depending on the substituent; the IRC path changes from rearrangement to fragmentation when substituent X becomes more electron donating. Ab initio dynamics simulations were found to follow the IRC path for X ¼ p-NH 2 and p-MeO giving fragmentation products, and almost so for X ¼ p-NO 2 giving the rearrangement products. However, in a borderline case where X is less donating than p-MeO or less withdrawing than p-NO 2 , the trajectories did not follow the minimum energy path on the potential energy surface, but gave both rearrangement and fragmentation products directly from the single TS. This is a novel example of path bifurcation for a closed shell anionic reaction. It was concluded that a reactivity-selectivity argument based on the traditional TS theory may not always be applicable even to a well-known textbook organic reaction.

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“…Moreover, as we make clear below, these spherical cylinders bound the true ''phase space reaction paths.'' The ability to compute these manifolds, and to track them far away from the transition region, is the key to the study of state-specific reactivity, 16,17 of dynamical effects on reactions 30,31 of control of reactivity 18,19 and as will be discussed below in more detail, of rare events.…”

Section: B the Dividing Surface The Nhim And Its Stable And Unstabmentioning

confidence: 99%

Phase space conduits for reaction in multidimensional systems: HCN isomerization in three dimensions

Waalkens

Burbanks

Wiggins

2004

The Journal of Chemical Physics

112

173

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The three-dimensional hydrogen cyanide/isocyanide isomerization problem is taken as an example to present a general theory for computing the phase space structures which govern classical reaction dynamics in systems with an arbitrary ͑finite͒ number of degrees of freedom. The theory, which is algorithmic in nature, comprises the construction of a dividing surface of minimal flux which is locally a ''surface of no return.'' The theory also allows for the computation of the global phase space transition pathways that trajectories must follow in order to react. The latter are enclosed by the stable and unstable manifolds of a so-called normally hyperbolic invariant manifold ͑NHIM͒. A detailed description of the geometrical structures and the resulting constraints on reaction dynamics is given, with particular emphasis on the three degrees of freedom case. A procedure is given which uses these structures to compute orbits homoclinic to, and heteroclinic between, NHIMs. The role of homoclinic and heteroclinic orbits in global recrossings of dividing surfaces and transport in complex systems is explained. The complete description provided here is inherently one within phase space; it cannot be inferred from a configuration space picture. A complexification of the classical phase space structures to incorporate quantum effects is also discussed. The results presented here call into question certain assumptions routinely made on the global dynamics; this paper provides methods that enable one to understand and quantify the phase space dynamics of reactions without making such assumptions.

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Dynamics-Driven Reaction Pathway in an Intramolecular Rearrangement

Cited by 152 publications

References 10 publications

Semiclassical nonadiabatic dynamics based on quantum trajectories for the O(P3,D1)+H2 system

Semiclassical nonadiabatic dynamics based on quantum trajectories for the O(P3,D1)+H2 system

Dynamic path bifurcation for the Beckmann reaction: observation and implication

Phase space conduits for reaction in multidimensional systems: HCN isomerization in three dimensions

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