Competition between collisions and optical pumping in unimolecular reactions induced by monochromatic infrared radiation

Duperrex, R.; Bergh, Hubert van den

doi:10.1016/0301-0104(79)85140-x

Cited by 44 publications

(1 citation statement)

References 72 publications

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“…The increase of radiation energy fluence up to 5.1 J/cm 2 increases Pbuf(1/e) almost by 2.5 times, approximately up to 40 Torr. 79 Comparing the experimental dependence /3 =/3 (Pbur) with those calculated by the model it is possible to find a number of excitation parameters including the value of (AE). In the case of CF2CFC1 mixed with Ar s such comparison…”

Section: Multiple Photon Ir Laser Physics Chemistry IV 357mentioning

confidence: 99%

Multiple Photon Infrared Laser Photophysics and Photochemistry. IV

et al. 1984

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This paper is the fourth in series of reviews on multiple photon IR laser photophysics and photochemistry. Unimolecular reactions of MP excited molecules and the isotopic selectivity of MP dissociation are considered. Contents 7. Unimolecular Reactions of Molecules Excited by IR Laser Radiation 313 7.1. Characteristics of IR multiple photon dissociation 314 7.1.1. Experimental methods of IR multiple photon dissociation investigation 316 7.1.2. Dependence of MP dissociation yield and quantum efficiency on laser pulse energy fluence and absorbed energy 319 7.1.3. Dependence of dissociation yield on IR laser frequency 323 7.1.4. MP dissociation in two-frequency IR field 326 7.2. Products of IR multiple photon dissociation and their energy distribution 330 311 312 V.N. BAGRATASHVILI et. al. 7.2.1. MP dissociation channels and primary fragments 330 7.2.2. Energy distribution of MP dissociation products 337 7.2.3. Visible luminescence in the case of MP IR excitation of molecules 342 7.3. Isomerization of multiple photon excited molecules 344 7.3.1. Experimental results for various molecules 346 7.3.2. Mechanisms of IR laser-induced isomerization 352 7.4. Role of collisional processes in IR multiple photon dissociation 354 7.4.1. Collisions with buffer gas 7.4.2. Collisions between excited molecules 7.4.3. Secondary reactions 8. Isotopic Selectivity of Multiple Photon IR Dissociation of Molecules 8.1. Characteristics of isotopically-selective MP dissociation 8.1.1. Kinetics of enrichment of two-component mixture 8.1.2. Experimental methods for selectivity parameters measurements 8.2. Resonant properties of selectivity 8.2.1. Dependence of MP dissociation selectivity on IR laser frequency 8.2.2. Selectivity of multiple photon absorption 8.2.3. Selectivity of MP excitation and dissociation for a small isotope shift 8.3. Ultimate spectral selectivity of MP dissociation. Gas temperature effect 8.4. Role of laser pulse intensity. Two-frequency MP dissociation 8.5. Effects of collisions on the selectivity of MP dissociation 397 8.5.1. Dependence of selectivity on parent gas pressure and relative isotope content 8.5.2. Role of V-V exchange 8.5.3. Collisions with buffer gas. Effect of V-T and rotational relaxation 412 8.6. Loss of MP dissociation selectivity in secondary chemical processes 418 MULTIPLE PHOTON IR LASER PHYSICS. CHEMISTRY IV 313 7. UNIMOLECULAR REACTIONS OF MOLECULES EXCITED BY IR LASER RADIATION observed. The basic parameters which characterize quantitatively the process of MP dissociation are dissociation yield/3 and its quantum efficiency flD/: (g is the average value of absorbed energy, D is the bond breaking energy). The dissociation yield is defined as a fraction of molecules dissociating per laser pulse on the gas volume under irradiation. In many works consideration has been given to the dependence of/3 and on laser radiation frequency fl, pulse energy fluence , energy absorbed by a molecule , etc. The effect of MP dissociation for the molecules acted upon with two successive IR pulses of different MULTIP...

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Section: Multiple Photon Ir Laser Physics Chemistry IV 357mentioning

confidence: 99%

Multiple Photon Infrared Laser Photophysics and Photochemistry. IV

et al. 1984

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Reaction Dynamics and Statistical Mechanics of the Preparation of Highly Excited States by Intense Infrared Radiation

Qüack

1982

Advances in Chemical Physics

100

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Master equations for photochemistry with intense infrared light (III) the influence of molecular parameters in URIMIR

Qüack

1979

Ber Bunsenges Phys Chem

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The influence of molecular parameters on the rate of unimolecular reactions induced by monochromatic infrared radiation (URIMIR) is considered in the range of validity of a Pauli master equation. Solutions of the master equation are obtained for a model series of bond fission reactions. A two parameter activation equation for the time dependent rate coefficient is established. The dependence of the steady state rate coefficient, the activation time, and further relevant rate parameters upon the threshold energy for reaction, the excitation quantum, the number of vibrational modes, and the integrated oscillator strength of the fundamental transition is established and summarized in three simple rules. Quantitative calculations for the case B intensity fall‐off are presented. The possibility of an absolute estimate of the rate parameters is discussed with the example of the URIMIR of CF3I.

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Competition between collisions and optical pumping in unimolecular reactions induced by monochromatic infrared radiation

Cited by 44 publications

References 72 publications

Multiple Photon Infrared Laser Photophysics and Photochemistry. IV

Multiple Photon Infrared Laser Photophysics and Photochemistry. IV

Reaction Dynamics and Statistical Mechanics of the Preparation of Highly Excited States by Intense Infrared Radiation

Master equations for photochemistry with intense infrared light (III) the influence of molecular parameters in URIMIR

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