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Full-Text Articles in Physics
Semiclassical Application Of The Mo/Ller Operators In Reactive Scattering, Sophya V. Garashchuk, J. C. Light
Semiclassical Application Of The Mo/Ller Operators In Reactive Scattering, Sophya V. Garashchuk, J. C. Light
Faculty Publications
Mo/ller operators in the formulation of reaction probabilities in terms of wave packet correlation functions allow us to define the wave packets in the interaction region rather than in the asymptotic region of the potential surface. We combine Mo/ller operators with the semiclassical propagator of Herman and Kluk. This does not involve further approximations and can be used with any initial value representation (IVR) semiclassical propagator. Time propagation in asymptotic regions of the potential due to Mo/ller operators reduces the oscillations of the propagator integrand and improves convergence of the results with respect to the number of trajectories. The effectiveness …
Cumulative Reaction Probability In Terms Of Reactant-Product Wave Packet Correlation Functions, Sophya V. Garashchuk, D. J. Tannor
Cumulative Reaction Probability In Terms Of Reactant-Product Wave Packet Correlation Functions, Sophya V. Garashchuk, D. J. Tannor
Faculty Publications
We present new expressions for the cumulative reaction probability (N(E)), cast in terms of time-correlation functions of reactant and product wave packets. The derivation begins with a standard trace expression for the cumulative reaction probability, expressed in terms of the reactive scattering matrix elements in an asymptotic internal basis. By combining the property of invariance of the trace with a wave packet correlation function formulation of reactive scattering, we obtain an expression for N(E) in terms of the correlation matrices of incoming and outgoing wave packets which are arbitrary in the internal coordinates. This formulation, like other recent formulations of …
Correlation Function Formulation For The State Selected Total Reaction Probability, Sophya V. Garashchuk, D. J. Tannor
Correlation Function Formulation For The State Selected Total Reaction Probability, Sophya V. Garashchuk, D. J. Tannor
Faculty Publications
A correlation function formulation for the state-selected total reaction probability, Nα(E), is suggested. A wave packet, correlating with a specific set of internal reactant quantum numbers, α, is propagated forward in time until bifurcation is complete at which time the nonreactive portion of the amplitude is discarded. The autocorrelation function of the remaining amplitude is then computed and Fourier transformed to obtain a reactivity spectrum. Dividing by the corresponding spectrum of the original, unfiltered, wave packet normalizes the reactivity spectrum, yielding the total reaction probability from the internal state, α. The procedure requires negligible storage and just one time-energy Fourier …