Quantum mechanical study of the unimolecular dissociation of HO2: A rigorous test of RRKM theory

Dobbyn, Abigail J.; Stumpf, Michael; Keller, Hans-Martin; Hase, William L.; Schinke, Reinhard

doi:10.1063/1.469320

Cited by 60 publications

(66 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Such a fluctuation is a manifestation of prominent quantum interference effects between overlapping resonances. This fluctuating behavior has also been obtained from Jϭ0 theoretical calculations on HO 2 dissociation by several groups, 13,26,31 which indicates that the dissociation of HO 2 is essentially irregular. Although experimental data are still not available for this system, fluctuating resonance rates have been observed for several other dissociation systems including H 2 CO, CH 3 O, and NO 2 .…”

Section: B Bound and Resonance Energiesmentioning

confidence: 89%

Calculation of bound and resonance states of HO2 for nonzero total angular momentum

Zhang

Smith

2003

The Journal of Chemical Physics

View full text Add to dashboard Cite

Bound and resonance states of HO 2 have been calculated quantum mechanically by the Lanczos homogeneous filter diagonalization method ͓Zhang and Smith, Phys. Chem. Chem. Phys. 3, 2282 ͑2001͒; J. Chem. Phys. 115, 5751 ͑2001͔͒ for nonzero total angular momentum Jϭ1,2,3. For lower bound states, agreement between the results in this paper and previous work is quite satisfactory; while for high lying bound states and resonances these are the first reported results. A helicity quantum number ⍀ assignment ͑within the helicity conserving approximation͒ is performed and the results indicate that for lower bound states it is possible to assign the ⍀ quantum numbers unambiguously, but for resonances it is impossible to assign the ⍀ helicity quantum numbers due to strong mixing. In fact, for the high-lying bound states, the mixing has already appeared. These results indicate that the helicity conserving approximation is not good for the resonance state calculations and exact quantum calculations are needed to accurately describe the reaction dynamics for HO 2 system. Analysis of the resonance widths shows that most of the resonances are overlapping and the interferences between them lead to large fluctuations from one resonance to another. In accord with the conclusions from earlier Jϭ0 calculations, this indicates that the dissociation of HO 2 is essentially irregular.

show abstract

Section: B Bound and Resonance Energiesmentioning

confidence: 89%

Calculation of bound and resonance states of HO2 for nonzero total angular momentum

Zhang

Smith

2003

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…For a classically chaotic system, these statistics can be derived from random matrix theory. In recent years, such a random matrix approach has been successfully used to model the statistics of resonances [4] and cross-section fluctuations in the photodissociation of classically chaotic molecules [8,9,10,11,12,13]. A semiclassical treatment was discussed in Refs.…”

mentioning

confidence: 99%

Fano interference and cross-section fluctuations in molecular photodissociation

et al. 2006

View full text Add to dashboard Cite

We derive an expression for the total photodissociation cross section of a molecule incorporating both indirect processes that proceed through excited resonances, and direct processes. We show that this cross section exhibits generalized Beutler-Fano line shapes in the limit of isolated resonances. Assuming that the closed system can be modeled by random matrix theory, we derive the statistical properties of the photodissociation cross section and find that they are significantly affected by the direct processes. We identify a unique signature of the direct processes in the cross-section distribution in the limit of isolated resonances.

show abstract

“…Such a fluctuation is a manifestation of prominent quantum interference effects between overlapping resonances. This fluctuating behavior has also been obtained from Jϭ0 theoretical calculations on HO 2 dissociation by several groups, 12,28,54 which indicates that the dissociation of HO 2 is essentially irregular. Although experimental data are still not available for this system, fluctuating resonance rates have been observed for several other dissociation systems including H 2 CO, CH 3 O, and NO 2 .…”

Section: B Bound and Resonance Energies "Rates…mentioning

confidence: 89%

“…For more broad resonances, this interpretation can be ambiguous. However, for simplicity we will use the term ''rates'' for the whole energy range, following the work by Schinke et al 12,54 In Fig. 2 we have plotted the quantum J ϭ10 specific dissociation rates for HO 2 →HϩO 2 in the energy range from 2.114 eV to 2.348 eV.…”

Section: B Bound and Resonance Energies "Rates…mentioning

confidence: 99%

Converged quantum calculations of HO2 bound states and resonances for J=6 and 10

Zhang

Smith

2004

The Journal of Chemical Physics

View full text Add to dashboard Cite

Accurate quantum calculation of the bound and resonant rovibrational states of Li − ( H 2 ) J. Chem. Phys. 122, 124318 (2005) Bound and resonance states of HO 2 are calculated quantum mechanically using both the Lanczos homogeneous filter diagonalization method and the real Chebyshev filter diagonalization method for nonzero total angular momentum Jϭ6 and 10, using a parallel computing strategy. For bound states, agreement between the two methods is quite satisfactory; for resonances, while the energies are in good agreement, the widths are in general agreement. The quantum nonzero-J specific unimolecular dissociation rates for HO 2 are also calculated.

show abstract

Quantum mechanical study of the unimolecular dissociation of HO2: A rigorous test of RRKM theory

Abstract: A quantitative test of unimolecular rate theory in the multiphoton dissociation of CF2CFCl

Cited by 60 publications

References 27 publications

Calculation of bound and resonance states of HO2 for nonzero total angular momentum

Calculation of bound and resonance states of HO2 for nonzero total angular momentum

Fano interference and cross-section fluctuations in molecular photodissociation

Converged quantum calculations of HO2 bound states and resonances for J=6 and 10

Contact Info

Product

Resources

About