Translational Energy-Distribution in the Products of Some Exothermic Reactions

Anlauf, K. G.; Charters, P. E.; Horne, David S.; Macdonald, R. Glen; Maylotte, D. H.; Polanyi, J. C.; Skrlac, W.J.; Tardy, D. C.; Woodall, K.B.

doi:10.1063/1.1673882

Cited by 90 publications

(3 citation statements)

References 8 publications

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“…The number above each peak represents the product vibrational state v', and the area under each curve gives the value of the relative rate constant kv,(T ) at room temperature. These theoretical results are in qualitative agreement with the reported experimental results [17].…”

Section: Classical Trajectory Calculationssupporting

confidence: 94%

Monte Carlo calculations of reaction rates and energy distributions among reaction products, F+D₂→DF+D

Wilkins

1974

Molecular Physics

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A three-dimensional classical trajectory analysis is used to determine the reaction dynamics of the reaction F + D2(v, J) -+DF(v', J') + D on an assumed London-Eyring-Polanyi-Sato (LEPS) potential energy surface. Monte Carlo procedures are used to start each collision trajectory. An analysis is presented of the dependences of the total reaction cross sections ar and specific reaction cross sections a(v, J, v', E1Q on the relative translational energy and initial vibrational and rotational energy of the reagent molecule D2(v, J). Data are presented of the temperature dependences of (1) the vibrational, rotational and translational energy distributions of the reaction products and (2) the rate constants for formation of DF in specific vibrational and rotational states. The probability that direct reaction between atomic fluorine and molecular deuterium will lead to formation of DF in the v'=0 state was found to be zero. The ratio k(v'=4)/h(v'=3) appears to be independent of temperature and has a value of 0"65, which is in excellent agreement with recent infra-red chemiluminescence experimental data.The ratio k(v'=2)/h(v'=3) has a slight temperature dependence and, at room temperature, has a value of 0"28. The ratio k(v'=l)/k(v'=3) was assumed independent of temperature and was assigned a value of 0"08. The results are compared with available experimental data and with previous theoretical studies.

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Section: Classical Trajectory Calculationssupporting

confidence: 94%

Monte Carlo calculations of reaction rates and energy distributions among reaction products, F+D₂→DF+D

Wilkins

1974

Molecular Physics

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“…"Continuum detailed rate constants," appropriate to molecular-beam experiments, can be obtained from these stick diagrams by the introduction of a Jacobian factor (2J+1)-1. 2 The translational energy of the reagents is more properly represented by a distribution of translational energies, since the spread in collision energies introduces a distribution in E tot '. The half-width at half-height of this distribution may be estimated from Monte Carlo trajectory studies on an LEPS surface for Cl+ HJ.6° This half-width is generally of the order of RT.1.61 Translational distributions for the reaction products can be obtained in which Etot' is given this ha1£width.…”

Section: Discussionmentioning

confidence: 99%

“…I5 ,I6 Product tional energy among the products of a number of vibrational energy distributions have' also been obexothermic reactions.1. 2 The distribution of vibrational tained from chemical laser studies. I7 -22 By careful energy in the H+CI2-+HClt+CI reaction was the control of the rotational temperature of the reactant first to be measured using the infrared chemilumines-molecule, conditions were achieved for which two cence technique.…”

Section: Introductionmentioning

confidence: 99%

Energy Distribution Among Reaction Products. IV. X+HY (X ≡ Cl, Br; Y ≡ Br, I), Cl+DI

Maylotte

Polanyi

Woodall

1972

The Journal of Chemical Physics

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190

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The distribution of vibrational, rotational, and translational energies (symbolized by V′, R′, and T′) have been obtained for the products of the isotopic pair of reactions Cl + HI → HCl + I and Cl + DI → DCl + I. The experimental method was the ``arrested relaxation'' variant of the infrared chemiluminescence technique. Detailed rate constants k(V′, R′, T′) are reported in the form of contour plots for these reactions. The total detailed rate constants into specified vibrational quantum states for Cl+HI (summed over the rotational levels of each v′ level) are k(v′ = 1) = 0.22, k(v′ = 2) = 0.35, [k(v′ = 3) = 1.00], k(v′ = 4) = 0.74; and for Cl + DI, k(v′ = 1) ≈ 0.08, k(v′ = 2) = 0.14, k(v′ = 3) = 0.35, k(v′ = 4) = 0.73, [k(v′ = 5) = 1.00], k(v′ = 6) = 0.05 [relative to the highest rate constant k(v̂′) = 1.00, in each case]. Preliminary energy distributions are also reported for the products of two other reactions, Cl + HBr → HCl + Br and Br + HI → HBr + I, in the X + HY → HX + Y family (X and Y are halogen atoms). The members of this family of reactions channel a substantial fraction of the energy available to the products into vibrational and rotational excitation, and only a small fraction into relative translation. For the Cl+HI and also the Cl+DI reaction the fractions are f̄V′ + f̄R′ (= 0.71 + 0.13) = 0.84; in contrast to f̄T′ = 0.16. As a corollary there is a marked inverse correlation between vibrational and rotational excitation in the reaction products. Despite the fact that the detailed rate constants into specified product quantum states [k(v′, J′)] are markedly different for the isotopic pair of reactions, the fractional conversion of the available energy into vibration, rotation, and translation are in close agreement (to ∼ ± 1%). This close parallelism in f̄V′, f̄R′, f̄T′ is in accord with predictions from classical trajectory studies. It indicates the usefulness of such calculations even for the case of reactions which yield products with widely spaced (vibrational and rotational) quantum levels.

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Chemiluminescence

Bronstein¹,

Kricka

Givens

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Chemiluminescence is the emission of light from chemical reactions at ordinary temperatures. The reactions of chemiluminescence produce a reaction intermediate or product in an electronically excited state, and radiative decay of the excited state is the source of the light. Chemiluminescence relates to fundamental molecular interactions and transformations and its study provides access to basic elements of reaction mechanisms and molecular properties, efficient chemiluminescence can provide an emergency or portable light source, chemiluminescence provides means to detect and measure trace elements and pollutants for environmental control or clinically important substances, and classification of the bioluminescent relationship between different organisms defines their biological relationship and pattern of evolution. Liquid‐phase, gas‐phase, and solid‐phase chemiluminescence are discussed as well as bioluminescence, which is characteristic of numerous marine and a few land organisms. The applications of chemical light include marking and illumination and several types of analyses such as flow injection, hplc, direct metal, titration indicators, immunoassay, bacteria and biomass determination, and air pollution.

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Translational Energy-Distribution in the Products of Some Exothermic Reactions

Cited by 90 publications

References 8 publications

Monte Carlo calculations of reaction rates and energy distributions among reaction products, F+D₂→DF+D

Monte Carlo calculations of reaction rates and energy distributions among reaction products, F+D₂→DF+D

Energy Distribution Among Reaction Products. IV. X+HY (X ≡ Cl, Br; Y ≡ Br, I), Cl+DI

Chemiluminescence

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Translational Energy-Distribution in the Products of Some Exothermic Reactions

Cited by 90 publications

References 8 publications

Monte Carlo calculations of reaction rates and energy distributions among reaction products, F+D2→DF+D

Monte Carlo calculations of reaction rates and energy distributions among reaction products, F+D2→DF+D

Energy Distribution Among Reaction Products. IV. X+HY (X ≡ Cl, Br; Y ≡ Br, I), Cl+DI

Chemiluminescence

Contact Info

Product

Resources

About

Monte Carlo calculations of reaction rates and energy distributions among reaction products, F+D₂→DF+D

Monte Carlo calculations of reaction rates and energy distributions among reaction products, F+D₂→DF+D