Three-Body Recombination and Dissociation of Nitrogen: A Comparison between Theory and Experiment

Shui, Ven H.; Appleton, John P.; Keck, James C.

doi:10.1063/1.1674368

Cited by 64 publications

(14 citation statements)

References 30 publications

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“…20 There has been considerable discussion as to the rela- has been observed in low-temperature infrared experim e n t~,~~ direct measurements of the bond energies for Is, Bra, and cl3 are not available. 20 There has been considerable discussion as to the rela- has been observed in low-temperature infrared experim e n t~,~~ direct measurements of the bond energies for Is, Bra, and cl3 are not available.…”

Section: Discussionmentioning

confidence: 99%

Gas-phase recombination of chlorine atoms

Widman¹,

DeGraff²

1973

J. Phys. Chem.

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Publication costs assisted by Madison CollegeThe recombination of chlorine atoms in the presence of various chaperons has been studied over the range 195-373°K using kinetic spectroscopy. The rate coefficients obtained, in M -2 sec-l units and expressed as kM = A exp(E/RT) or log kM = B + C log T, were kHe = 1.47 x lo9 exp(260 f 10IRT) or log kHe = 10.55 f 0.12 -(0.48 f 0.009) log T; k~~ = 1.26 X lo9 exp(660 f 20/RT) or log k~~ = 12.74 f 0.26 -(1.27 f 0.02) log T; kAr = 2.5 x los exp(1800 f 50/RT) or log kAr = 18.62 f 0.60 -(3.59 f 0.05) log T; k N z = 5.8 X lo8 exp(1600 f 140/RT) or log kNz = 15.61 f 0.65 -(2.32 f 0.02) log T; ksF6 = 2.4 x lo9 exp(970 f 100/RT) or log ksF6 = 13.72 f 0.76 -(1.47 f 0.02) log T; kCFi = l.62 x log exp(1200 f 200/RT) or log kCF4 = 14.43 f 1.36 -(1.77 f 0.04) log T; kcoz = 1.56 x 109 exp(1500 f 200/RT) or log kcOz = 15.75 f 0.60 -(2.22 f 0.018) log T. Where comparison values are available they are in good agreement with the results of this investigation. The values reported here are compared with the available data for iodine and bromine atom recombination.

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Section: Discussionmentioning

confidence: 99%

Gas-phase recombination of chlorine atoms

Widman¹,

DeGraff²

1973

J. Phys. Chem.

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“…Shui, Appleton, and Keck 14 give the condition for a relaxed complex formed via (3.1a) and (3.1b) as (3.6) where EMX is the depth of the MX potential well. If M were chemically reactive, so that MX had manv bound levels, one might expect the lowest levels of MX to be populated so slowly that they would contribute negligibly to the recombination rate.…”

Section: Bound-complex Mechanismmentioning

confidence: 99%

On the Mechanism of Low-Temperature Termolecular Atomic Recombination

Pack

Snow

Smith

1972

The Journal of Chemical Physics

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Articles you may be interested inLow-temperature noncontact atomic-force microscope with quick sample and cantilever exchange mechanism Rev.A simple theory of gas-phase termolecular atomic recombination kinetics is presented which treats the bound-complex (BC) mechanism in a fashion which parallels the Roberts, Bernstein, and Curtiss resonance theory of the energy-transfer (ET) mechanism. The ET rate constant has a low temperature maximum, but the BC rate constant does not. The contributions of the two mechanisms to the low-temperature recombination of hydrogen atoms, with He, Ar, and H2 as third bodies, are estimated and compared. The presence (absence) of a low-temperature maximum in the observable total rate constant is determined by absence (presence) of bound vibrational levels of the hydrogen-third body van der Waals dimer. Hence, experimental studies of these reactions could yield valuable information about the interatomic potentials.

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“…10,11 Indeed, several early works found evidence that dissociation caused significant depletion of the high vibrational levels (resulting in non-Boltzmann energy distributions), because molecules in such levels were favored to dissociate. 6,12,13 Finally, still more advanced models, such as the Morse potential model of Johnston and Birks with all transitions allowed, 3 the forced harmonic oscillator (FHO) framework of Adamovich et al, [14][15][16][17] and the information-theoretic approach of Gonzales and Varghese, [18][19][20] permitted both multiquantum transitions and dissociation from any vibrational level. We could also include in this category the analytic model of Macheret and Rich, 21 which assumes classical, impulsive collisions between molecules and a "threshold function" for the minimum translational energy needed for a dissociative collision.…”

Section: Introductionmentioning

confidence: 99%

An improved potential energy surface and multi-temperature quasiclassical trajectory calculations of N2 + N2 dissociation reactions

Bender

Valentini

Nompelis

et al. 2015

The Journal of Chemical Physics

200

141

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Accurate modeling of high-temperature hypersonic flows in the atmosphere requires consideration of collision-induced dissociation of molecular species and energy transfer between the translational and internal modes of the gas molecules. Here, we describe a study of the N2 + N2⟶N2 + 2N and N2 + N2⟶4N nitrogen dissociation reactions using the quasiclassical trajectory (QCT) method. The simulations used a new potential energy surface for the N4 system; the surface is an improved version of one that was presented previously. In the QCT calculations, initial conditions were determined based on a two-temperature model that approximately separates the translational-rotational temperature from the vibrational temperature of the N2 diatoms. Five values from 8000 K to 30,000 K were considered for each of the two temperatures. Over 2.4 × 10(9) trajectories were calculated. We present results for ensemble-averaged dissociation rate constants as functions of the translational-rotational temperature T and the vibrational temperature T(v). The rate constant depends more strongly on T when T(v) is low, and it depends more strongly on T(v) when T is low. Quasibound reactant states contribute significantly to the rate constants, as do exchange processes at higher temperatures. We discuss two sets of runs in detail: an equilibrium test set in which T = T(v) and a nonequilibrium test set in which T(v) < T. In the equilibrium test set, high-v and moderately-low-j molecules contribute most significantly to the overall dissociation rate, and this state specificity becomes stronger as the temperature decreases. Dissociating trajectories tend to result in a major loss of vibrational energy and a minor loss of rotational energy. In the nonequilibrium test set, as T(v) decreases while T is fixed, higher-j molecules contribute more significantly to the dissociation rate, dissociating trajectories tend to result in a greater rotational energy loss, and the dissociation probability's dependence on v weakens. In this way, as T(v) decreases, rotational energy appears to compensate for the decline in average vibrational energy in promoting dissociation. In both the equilibrium and nonequilibrium test sets, in every case, the average total internal energy loss in the dissociating trajectories is between 10.2 and 11.0 eV, slightly larger than the equilibrium potential energy change of N2 dissociation.

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Three-Body Recombination and Dissociation of Nitrogen: A Comparison between Theory and Experiment

Cited by 64 publications

References 30 publications

Gas-phase recombination of chlorine atoms

Gas-phase recombination of chlorine atoms

On the Mechanism of Low-Temperature Termolecular Atomic Recombination

An improved potential energy surface and multi-temperature quasiclassical trajectory calculations of N2 + N2 dissociation reactions

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