Unimolecular dissociation of HOCl: unexpectedly broad distribution of rate constants

Hauschildt, J.; Weiss, J.; Beck, Christian; Grebenshchikov, Sergy Yu.; Düren, R.; Schinke, Reinhard; Koput, Jacek

doi:10.1016/s0009-2614(98)01432-8

Cited by 38 publications

(39 citation statements)

References 28 publications

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“…We will not offer such an analysis here and assume (12) on the grounds of simplicity alone. This may be formalised by noting that (12) minimises the information content [17,18] I [P (x)] = P (x) ln P (x) dx, subject to the constraint that the correlations are as written in (6) and that N is large. Minimisation of information is not a proof, however, and ultimately we rely on detailed numerical testing to justify the choice of distribution.…”

Section: A a Gaussian Hypothesismentioning

confidence: 99%

Scarring and the Statistics of Tunnelling

Creagh¹,

Lee²,

Whelan

2002

Annals of Physics

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We show that the statistics of tunnelling can be dramatically affected by scarring and derive distributions quantifying this effect. Strong deviations from the prediction of random matrix theory can be explained quantitatively by modifying the Gaussian distribution which describes wavefunction statistics. The modified distribution depends on classical parameters which are determined completely by linearised dynamics around a periodic orbit. This distribution generalises the scarring theory of Kaplan [Phys. Rev. Lett. 80, 2582(1998] to describe the statistics of the components of the wavefunction in a complete basis, rather than overlaps with single Gaussian wavepackets. In particular it is shown that correlations in the components of the wavefunction are present, which can strongly influence tunnellingrate statistics. The resulting distribution for tunnelling rates is tested successfully on a two-dimensional double-well potential.

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Section: A a Gaussian Hypothesismentioning

confidence: 99%

Scarring and the Statistics of Tunnelling

Creagh¹,

Lee²,

Whelan

2002

Annals of Physics

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“…3 of Ref. [19]). As the rotational quantum number J is tuned up to large values, the width shows a pronounced resonance-like maximum around J ϭ 25Ϫ 27 ( Fig.…”

Section: Resultsmentioning

confidence: 88%

“…The remarkable degree of regularity leads to a pronounced mode specific behavior of the dissociation dynamics, which, in turn, implies a wide distribution of dissociation rates spanning a range over several orders of magnitude near threshold [19]. Because of the very weak coupling of HO stretching to the other two modes, states with large excitation in mode ν 1 are among those, which have the smallest resonance widths Γ (i.e., longest lifetimes τ ϭ ប/Γ).…”

Section: Introductionmentioning

confidence: 99%

Influence of Vibrational Resonances and Coriolis Coupling on Dissociation Rates in the Near-threshold Unimolecular Fragmentation of HOCl

Hauschildt¹,

Weiss²,

Schinke³

2000

Zeitschrift Für Physikalische Chemie

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The unimolecular dissociation of HOCl in the ground electronic state near the HOϩCl fragmentation threshold is investigated employing an ab initio potential energy surface. The dynamics calculations are performed by using an imaginary absorbing potential and filter diagonalization. The computational study is mainly focused on the influence of accidental or systematic vibrational resonances on the total angular momentum dependence of dissociation rates and the importance of Coriolis interaction.

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“…where H (1,2) m are Hankel functions and k m = √ S so that B = S · A, where B(A) is a column matrix containing amplitudes B m (A m ). The scattering matrix can be written as (1) .…”

Section: Reaction Matrix Theorymentioning

confidence: 99%

“…Recent studies of the molecule HOCl, in the electronic ground state, reveal quasibound states at energies above the HO + Cl dissociation energy that have lifetimes ranging over several orders of magnitude [1][2][3][4]. These studies are all based on the use of absorbing potentials to locate quasibound states.…”

Section: Introductionmentioning

confidence: 99%

Quasibound states in a chaotic molecular system

Barr

Reichl

2011

Phys. Rev. A

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We show the influence of stable and unstable periodic orbits on the energy eigenstates of the HOCl molecule, both below and above dissociation. The energy range considered is low enough to hold the HO bond fixed, allowing a two-dimensional model of the molecule. Above dissociation unstable periodic orbits, in a chaotic sea, anchor quasibound states of the molecule. Quasibound states are calculated using reaction matrix theory and are found to have lifetimes ranging over five orders of magnitude.

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Unimolecular dissociation of HOCl: unexpectedly broad distribution of rate constants

Cited by 38 publications

References 28 publications

Scarring and the Statistics of Tunnelling

Scarring and the Statistics of Tunnelling

Influence of Vibrational Resonances and Coriolis Coupling on Dissociation Rates in the Near-threshold Unimolecular Fragmentation of HOCl

Quasibound states in a chaotic molecular system

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