Reactive scattering with row-orthonormal hyperspherical coordinates. 4. Four-dimensional-space Wigner rotation function for pentaatomic systems

Kuppermann, Aron

doi:10.1039/c0cp02907f

Cited by 11 publications

(7 citation statements)

References 43 publications

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“…The use of coordinates better adapted to treat the high symmetry of the system, such as the hyperspherical formalism recently developed by Kuppermann [43,45], is also envisaged.…”

Section: Discussionmentioning

confidence: 99%

“…For this aim, proper coordinates should be designed, like the democratic hyperspherical coordinates developed recently by Kuppermann [43]. The use of these coordinates requires the evaluation of the hyperspherical harmonics, still in development [44,45]. Another set of symmetric coordinates was developed to study the spectroscopy of H 5 + and isotopomers [36,46,47], with respect to an equilibrium geometry.…”

Section: Hmentioning

confidence: 99%

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Simulation of the infrared predissociation spectra of H5+

et al. 2012

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A quantum study of the bound states and infrared predissociation spectra of H 5 + is done using a recently proposed global and accurate potential-energy surface [Aguado et al., J. Chem. Phys. 133, 024306 (2010)]. The bound states are calculated for seven degrees of freedom using an iterative Lanczos method, yielding a dissociation energy in very good agreement with the available experimental data. The predissociation states are described by a wave-packet treatment considering a shared-proton model, in which the three-dimensional motion of the central atom is described using non-Jacobi bond coordinates. The justification of this model is that the change in the electric dipole moment is larger as a function of the motion of the central atom, responsible for the proton transfer in the H 3 + + H 2 → H 2 + H 3 + reaction. The electric dipole moment is calculated at the level of coupled-cluster theory with single and double excitations and fitted in nine dimensions to an analytical function. With it, the infrared predissociation spectrum is simulated, yielding a reasonable agreement with recent measurements.

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“…The use of coordinates better adapted to treat the high symmetry of the system, such as the hyperspherical formalism recently developed by Kuppermann [43,45], is also envisaged.…”

Section: Discussionmentioning

confidence: 99%

Section: Hmentioning

confidence: 99%

Simulation of the infrared predissociation spectra of H5+

et al. 2012

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“…(44) and comes from the expansion of the hyperangular kinetic energy Eq. (20). H C 2 , The last two terms of Eq.…”

Section: A Coordinate System and Coulomb Interactionmentioning

confidence: 99%

Hyperspherical Asymptotics of a System of Four Charged Particles

Daily

2015

Few-Body Syst

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“…36 The use of these coordinates requires the evaluation of the hyperspherical harmonics, a work still in progress. 37,38 One of the first simulations of the title reaction was the quasi-classical study performed by Moyano and Collins, 34 who found discrepancies with the available experimental results, which were attributed to possible quantum effects and to the accuracy of the PES. Recently seven-degree-of-freedom quantum scattering calculations of the H 2 + H 2 D + reaction have been reported, 39 for state-selected initial states, which do not take into account the permutation symmetry.…”

Section: Introductionmentioning

confidence: 99%

Dynamically biased statistical model for the ortho/para conversion in the ${\rm H}_2 + {\rm H}_3^+$H2+H3+ → ${\rm H}_3^{+} +$H3++ H2 reaction

Gómez-Carrasco

González-Sánchez

Aguado

et al. 2012

The Journal of Chemical Physics

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In this work we present a dynamically biased statistical model to describe the evolution of the title reaction from statistical to a more direct mechanism, using quasi-classical trajectories (QCT). The method is based on the one previously proposed by Park and Light [J. Chem. Phys. 126, 044305 (2007)]. A recent global potential energy surface is used here to calculate the capture probabilities, instead of the long-range ion-induced dipole interactions. The dynamical constraints are introduced by considering a scrambling matrix which depends on energy and determine the probability of the identity/hop/exchange mechanisms. These probabilities are calculated using QCT. It is found that the high zero-point energy of the fragments is transferred to the rest of the degrees of freedom, what shortens the lifetime of H + 5 complexes and, as a consequence, the exchange mechanism is produced with lower proportion. The zero-point energy (ZPE) is not properly described in quasiclassical trajectory calculations and an approximation is done in which the initial ZPE of the reactants is reduced in QCT calculations to obtain a new ZPE-biased scrambling matrix. This reduction of the ZPE is explained by the need of correcting the pure classical level number of the H + 5 complex, as done in classical simulations of unimolecular processes and to get equivalent quantum and classical rate constants using Rice-Ramsperger-Kassel-Marcus theory. This matrix allows to obtain a ratio of hop/exchange mechanisms, α(T), in rather good agreement with recent experimental results by Crabtree et al. [J. Chem. Phys. 134, 194311 (2011)] at room temperature. At lower temperatures, however, the present simulations predict too high ratios because the biased scrambling matrix is not statistical enough. This demonstrates the importance of applying quantum methods to simulate this reaction at the low temperatures of astrophysical interest.

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Reactive scattering with row-orthonormal hyperspherical coordinates. 4. Four-dimensional-space Wigner rotation function for pentaatomic systems

Cited by 11 publications

References 43 publications

Simulation of the infrared predissociation spectra of H5+

Simulation of the infrared predissociation spectra of H5+

Hyperspherical Asymptotics of a System of Four Charged Particles

Dynamically biased statistical model for the ortho/para conversion in the ${\rm H}_2 + {\rm H}_3^+$H2+H3+ → ${\rm H}_3^{+} +$H3++ H2 reaction

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