Vibration-to-Translation (V–T) Energy Transfer in Gases

Yardley, James T.

doi:10.1016/b978-0-12-768550-2.50008-6

Cited by 89 publications

(146 citation statements)

References 50 publications

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“…We consider the fast and slow component separately and set where is the reduced mass of the collider pair and denotes the temperature [42]. In Figures 6 and 7, log⟨⟨ ⟩⟩ is plotted vs.…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

“…We use time-resolved detection of 3 NCN with LIF at 329.01 nm. The results are interpreted with a simple Landau-Teller/Schwartz-Slawsky-Herzfeld model [42][43][44], and in particular from the bath gas dependence, information on the mechanism of relaxation can be obtained. A kinetic model is proposed that is capable of describing the LIF intensity-time profiles observed.…”

Section: Ncnmentioning

confidence: 99%

“…First, for the rare gases both bim fast and bim slow decrease with increasing mass of the collider (with a small deviation in the case of Ne), which is quite a typical behavior for vibrational relaxation by vibration-to-translation ( -) energy transfer [42]. For the further discussion, it is advantageous to transform the rate coefficients to dimensionless transition probabilities per collision, ⟨⟨ ⟩⟩, by the relation [42] ⟨⟨ ⟩⟩ = (…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

“…For the further discussion, it is advantageous to transform the rate coefficients to dimensionless transition probabilities per collision, ⟨⟨ ⟩⟩, by the relation [42] ⟨⟨ ⟩⟩ = (…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

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Collisional Relaxation of NCN: An Experimental Study with Laser-Induced Fluorescence

Hetzler

Olzmann

2015

Zeitschrift Für Physikalische Chemie

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Collisional relaxation of NCN produced by photolysis of NCN 3 at a wavelength of 248 nm has been investigated with laser-induced fluorescence (LIF) in a temperature range of 240-293 K and a pressure range of 10-800 mbar with different bath gases (He, Ne, Ar, Kr, H 2 , N 2 , O 2 , and N 2 O). LIF excitation spectra were recorded, and LIF intensity-time profiles experimentally obtained at an excitation wavelength of 329.01 nm have been fitted with biexponential functions. The pressure and bath gas dependence of the rate coefficients obtained was rationalized in terms of a simple Landau-Teller/Schwartz-Slawsky-Herzfeld model, and notable influences of vibrational energy transfer to the rate of the overall relaxation process have been found. Evidence was obtained for a two-channel vibrational relaxation in NCN.

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Section: Mechanistic Considerationsmentioning

confidence: 99%

Section: Ncnmentioning

confidence: 99%

Section: Mechanistic Considerationsmentioning

confidence: 99%

Section: Mechanistic Considerationsmentioning

confidence: 99%

See 2 more Smart Citations

Collisional Relaxation of NCN: An Experimental Study with Laser-Induced Fluorescence

Hetzler

Olzmann

2015

Zeitschrift Für Physikalische Chemie

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“…Such near-resonant or resonant energy transfer is known to be the principal energy pathway in molecular collisions, ranging from diatomic to polyatomic molecules. 33,34 In Figure 7, The numbers in the parentheses are the % fraction of the total energy released in the reaction. 028, so the vibrational population distribution of OH produced on the silicon surface seriously deviates from the prediction of the Boltzmann distribution law.…”

Section: E Soh = ½M Smentioning

confidence: 99%

Formation of Hydroxyl Radical from the Hydrogen Chemisorbed Silicon Surface by Incident Oxygen Atoms

2003

Bulletin of the Korean Chemical Society

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We have calculated the probability of the OH formation and energy deposit of the reaction exothermicity in the newly formed OH, particularly in its vibrational motion, in the gas-surface reaction O(g) + H(ad)/Si ç OH(g) + Si on the basis of the collision-induced Eley-Rideal mechanism. The reaction probability of the OH formation increases linearly with initial excitation of the HSi vibration. The translational and vibrational motions share most of the energy when the H-Si vibration is initially in the ground state. But, when the initial excitation increases, the vibrational energy of OH rises accordingly, while the energies shared by other motions vary only slightly. The product vibrational excitation is significant and the population distribution is inverted. Flow of energy between the reaction zone and the solid has been incorporated in trajectory calculations. The amount of energy propagated into the solid is only a few percent of the available energy released in the OH formation.

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Quenching of I(2P�) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

Chiappero

Badini

Argüello

1997

Int. J. Chem. Kinet.

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I* emission. These have been extended to many systems to understand the mechanism involved in energy transfer processes. This problem has been tackled using several approaches: (a) Direct measurement of state-to-state E-v rate constants; (b) Temperature dependence of the bulk or overall quenching rate constants; (c) Isotope effects on the observed quenching rate constants; and (d) study of the quenching efficiencies of a "family" of compounds.Although the first approach is the most satisfactory and direct, only in few cases is it experimentally achievable. Few systems (HF, H 2 , and H 2 O) [5][6][7][8] have been studied directly (case a) because of the complexity added by the acceptor intramolecular energy redistribution which grows with the number of vibrational degrees of freedom. Based on the kinetic analysis of the system, state-to-state energy transfer studies are limited up to triatomic acceptor molecules. INTRODUCTIONThe study of the electronically excited iodine atom, I ( 2 P 1/2 ) (hereafter called I*) constitutes a case example of a system which can undergo electronic to vibrational-rotational energy transfer. The I* is only about 0.92 eV above the ground state and this energy excess hardly contributes to the already low reactivity of the iodine atom in gas phase. Actually, there are few systems in which reactive quenching of I* is present (i.e., interhalogens, ozone) [1 -4].Extensive studies have been carried out measuring quenching efficiencies of several compounds on the ABSTRACTThe deactivation of I( 2 P 1/2 ) by R-OH compounds (R ϭ H, C n H 2nϩ1 ) was studied using time-resolved atomic absorption at 206.2 nm. The second-order quenching rate constants determined for H 2 O, CH 3 OH, C 2 H 5 OH, n-C 3 H 7 OH, i-C 3 H 7 OH, n-C 4 H 9 OH, i-C 4 H 9 OH, s-C 4 H 9 OH, t-C 4 H 9 OH, are respectively, 2.4 Ϯ 0.3 ϫ 10 Ϫ12 , 5.5 Ϯ 0.8 ϫ 10 Ϫ12 , 8 Ϯ 1 ϫ 10 Ϫ12 , 10 Ϯ 1 ϫ 10 Ϫ12 , 10 Ϯ 1 ϫ 10 Ϫ12 , 11.1 Ϯ 0.9 ϫ 10 Ϫ12 , 9.8 Ϯ 0.9 ϫ 10 Ϫ12 , 7.1 Ϯ 0.7 ϫ 10 Ϫ12 , and 4.1 Ϯ 0.4ϫ 10 Ϫ12 cm 3 molec Ϫ1 s Ϫ1 at room temperature. It is believed that a quasi-resonant electronic to vibrational energy transfer mechanism accounts for most of the features of the quenching process. The influence of the alkyl group and its role in the total quenching rate is also discussed.

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Vibration-to-Translation (V–T) Energy Transfer in Gases

Cited by 89 publications

References 50 publications

Collisional Relaxation of NCN: An Experimental Study with Laser-Induced Fluorescence

Collisional Relaxation of NCN: An Experimental Study with Laser-Induced Fluorescence

Formation of Hydroxyl Radical from the Hydrogen Chemisorbed Silicon Surface by Incident Oxygen Atoms

Quenching of I(2P�) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

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