Statistical Theory of Chemical Kinetics : Application to Neutral-Atom—Molecule Reactions

Pechukas, Philip; Light, John C.; Rankin, C.

doi:10.1063/1.1726760

Cited by 455 publications

(145 citation statements)

References 23 publications

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“…Such a distribution could result if photoexcitation is followed by internal conversion to the ground-state surface, and the resulting microcanonical ensemble lives long enough for the available energy to be randomized among the vibrational modes of the molecule. To test this possibility, both the one-photon and multiphoton distributions are calculated using phase space theory (PST), 55 a reasonable statistical model to apply in the case of barrierless dissociation.…”

Section: Discussionmentioning

confidence: 99%

Photodissociation of Linear Carbon Clusters C_n (n = 4−6)

et al. 2000

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The photodissociation of mass-selected linear carbon clusters (C n , n ) 4-6) is studied using fast beam photofragment translational spectroscopy. The photofragment yield (PFY) spectra consist of several continua spanning the whole visible and ultraviolet region. The product mass distributions for dissociation of C n clusters are dominated by C 3 and its partner fragment C n-3 , although some minor channels are also identified for dissociation of C 4 and C 5 clusters. Translational energy P(E T ) distributions for the C 3 + C n-3 channel were measured at several photolysis energies. The PFY spectra and P(E T ) distributions indicate that multiphoton dissociation occurs at photon energies below the dissociation threshold and that both single-photon and multiphoton dissociation occur above the threshold. The one-photon components of the P(E T ) distributions can be modeled by phase space theory (PST), suggesting that photoexcitation is followed by internal conversion to the ground state. The PST analysis yields dissociation energies for C n f C 3 + C n-3 in reasonable agreement with recent Knudsen effusion mass spectrometry measurements.

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Section: Discussionmentioning

confidence: 99%

Photodissociation of Linear Carbon Clusters C_n (n = 4−6)

et al. 2000

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“…[33][34][35] If this is so, the total reaction probability, in Fig. 1 open channels in the product channels, in contrast to the few channels of OH + N reactants.…”

Section: A Reaction Probabilitiesmentioning

confidence: 99%

Accurate time dependent wave packet calculations for the N + OH reaction

Bulut

Roncero

Jorfi

et al. 2011

The Journal of Chemical Physics

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We present accurate quantum calculations of state-to-state cross sections for the N + OH → NO + H reaction performed on the ground 3 A global adiabatic potential energy surface of Guadagnini et al. [J. Chem. Phys. 102, 774 (1995)]. The OH reagent is initially considered in the rovibrational state v = 0, j = 0 and wave packet calculations have been performed for selected total angular momentum, J = 0, 10, 20, 30, 40,...,120. Converged integral state-to-state cross sections are obtained up to a collision energy of 0.5 eV, considering a maximum number of eight helicity components, = 0,...,7. Reaction probabilities for J = 0 obtained as a function of collision energy, using the wave packet method, are compared with the recently published time-independent quantum mechanical one. Total reaction cross sections, state-specific rate constants, opacity functions, and product state-resolved integral cross-sections have been obtained by means of the wave packet method for several collision energies and compared with recent quasi-classical trajectory results obtained with the same potential energy surface. The rate constant for OH(v = 0, j = 0) is in good agreement with the previous theoretical values, but in disagreement with the experimental data, except at 300 K.

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“…The comparison between phase space [84] statistical calculations [31], experimental data and dynamical studies of the title reaction have shown that the dynamics of the OH 2 complex plays an important role on the energy distribution of the products. The higher rotational energy of the products has already been noted by Buss et al [18] and has been explained as a result of the excitation of the vibrational bending mode due to the insertion mechanism.…”

Section: Product Energy Distributionsmentioning

confidence: 99%