Primary energy distribution in the products of the reaction F + HBr .fwdarw. HF(v') + Br

Aker, Pamela M.; Donaldson, D. J.; Sloan, J. J.

doi:10.1021/j100405a016

Cited by 37 publications

(36 citation statements)

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“…The PES calculations disfavour the reaction pathway to follow a C 3v end-on attack to abstract an H atom. Similar conclusions may also be found in other cases such as the Mg(3 1 P), Zn(4 1 P) [76][77][78], Cu(4 2 P) [79], O(2 1 D 2 ) [80][81][82], and N(2 2 D) [83] with CH 4 reactions.…”

supporting

confidence: 85%

Dynamical and stereodynamical studies of alkaline-earth atom–molecule reactions

Lin

Ureña

2007

International Reviews in Physical Chemistry

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Alkaline-earth atom molecule reactions have been extensively investigated since the early days of reaction dynamics. Though these reactions have many similarities to those of corresponding alkali atoms, as one would expect from their low ionization potential, there are important differences due to the presence of the two valence electrons in the alkaline-earth atom. This feature confers a distinct dynamical or stereodynamical behaviour whose basic description and analysis is the main objective of this article. The adopted approach is phenomenological based on the huge body of data revealed by modern crossed-beam and laser pump and probe techniques with no intention to be comprehensive but rather to put into context both authors' work. The paper starts with a resume´of the experimental approaches followed by a visit to full-collision studies under gas cell, beam-gas and crossed-beam arrangements. Detailed analysis and discussion is given of the M þ H 2 (M ¼ Ca, Mg) ! MH þ H reaction family whose dynamics is discussed using their Potential Energy Surfaces. In these studies care was taken to discuss the most relevant features of the molecular reaction dynamics with emphasis on the energy selectivity and on the stereodynamical (vectorial) nature of the reaction. To this end the available data are discussed in light of topological features of the underlying potential energy surface favouring either insertion or abstraction mechanisms. Particular attention is paid to the discussion of alkaline-earth atom reactions with halogen containing molecules. In these reactions the presence of two valence electrons leads to reaction channels, as chemiluminescent or chemi-ionization reactions, which are specifically associated with the transfer of the more energetic (inner harpooning) electron, whose dynamics or stereodynamics pattern differs from those of reaction channels associated to the transfer of the first, less energetic electron as, for example, in ion-pair reactions. A full section of the paper is dedicated to photo-induced intracluster reactions and, in particular, to the transition state dynamics of the prototype Ba . . . FCH 3 þ h ! BaF þ CH 3 reaction investigated in great detail by both nanosecond and femtosecond photo-ion and photo-electron pump and probe techniques. For this system the combination of these ultrahigh resolution techniques with isotopic labelling and ab initio calculations allowed the deciphering of its ultrafast reaction mechanism. Finally, the paper ends with some concluding remarks based on the observed propensity rules or general trends found in these alkaline-earth atom reactions.

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confidence: 85%

Dynamical and stereodynamical studies of alkaline-earth atom–molecule reactions

Lin

Ureña

2007

International Reviews in Physical Chemistry

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“…The nascent vibrational distributions of OH in reactions (R1) and (R4) are nearly identical, with an equal proportion of OH, B20%, formed in the ground vibrational state. [33][34][35][36][37][38][39][40][41] A direct comparison of the LIF signals by pumping A( 2 S 1 (u 0 ¼ 1)) ' X( 2 P i (u 00 ¼ 0)) gives then the OH-yield of (R1) if vibrational quenching of OH to its ground vibrational state and reactive removal are not interfering. These conditions were satisfied by working at a low total pressures of about…”

Section: Laser-induced Fluorescence Measurementsmentioning

confidence: 99%

“…The nascent vibrational population of OH for reaction (R1) is based on the LIF measurements by three research groups, two time-resolved Fourier transform infrared (TRFTIR) studies and a recent theoretical study, giving P(u ¼ 0 : 1 : 2 : 3 : 4) ¼ 0.21 : 0.21 : 0.26 : 0.21 : 0.11. 33,[36][37][38][39][40] For reaction (R4), a vibrational population of P(u ¼ 0 : 1 : 2 : 3 : 4) ¼ 0.21 : 0.22 : 0.24 : 0.21 : 0.12 is based on LIF measurements, two sets of TRFTIR results and a theoretical study. [34][35][36][37]40 All studies conclude a nascent ground vibrational population ratio for OH formed in reactions (R1) and (R4):…”

Section: Oh-yieldmentioning

confidence: 99%

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A temperature dependence kinetic study of O(1D) + CH4: overall rate coefficient and product yields

Vranckx

Peeters

Carl

2008

Phys. Chem. Chem. Phys.

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Using a recently-developed chemiluminescence technique for monitoring O(1D), the rate coefficient, k1, of the important atmospheric reaction O(1D) + CH4 --> products has been determined over a wide temperature range, 227 to 450 K. The rate coefficient was shown to be independent of temperature, having a value of (1.91 +/- 0.08) x 10(-10) cm3 s(-1); the quoted uncertainties are with 95% confidence. This highly precise value, based on an extended set of determinations with very low scatter, is significantly greater, 26%, than current recommended values. Secondly, the fraction of O(1D) quenched to O(3P) by CH4, k(1q)/k1, was precisely determined from chemiluminescence decays over the temperature range 236 to 340 K. A temperature independent value for k(1q)/k1 of 0.002 +/- 0.003 was found. Finally, LIF detection of OH has been applied to accurately determine the product branching fraction to OH of O(1D) + CH4 at room temperature. Our value, k(1a)/k1 = 0.76 +/- 0.08 (95% confidence), is in line with recent determinations by other groups.

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“…Thermal rate coefficients for the reactions of O( 1 D 2 ) with hydrocarbons are generally very large, 2 approaching those of gas kinetic values. The channel producing electronic ground-state OH (reaction 1) has been studied comprehensively using laserinduced fluorescence (LIF), 3 infrared chemiluminescence techniques, 4 and crossed molecular beam studies. 5 Reaction 1 is highly exothermic, releasing ~190 kJ mol −1 for CH 4 , and 200-220 kJ mol −1 for higher saturated hydrocarbons, 6 which is enough to produce vibrationally excited OH(X …”

Section: Introductionmentioning

confidence: 99%

Dynamics of OH Production in the Reaction of O(¹D₂) with Cyclopropane

Jang¹,

Jin²,

Kim³

et al. 2014

Bulletin of the Korean Chemical Society

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The OH(X 2 Π, υ" = 0,1) internal state distribution following the reaction of electronically excited oxygen atom (O( 1 D2)) with cyclo-C3H6 has been measured using laser-induced fluorescence, and compared with that following the reaction of O( 1 D2) with C3H8. The overall characteristics of the OH internal energy distributions for both reactions were qualitatively similar. The population propensity of the П(A′) Λ-doublet sub-level suggested that both reactions proceeded via an insertion/elimination mechanism. Bimodal rotational population distributions supported the existence of two parallel mechanisms for OH production, i.e., statistical insertion and nonstatistical insertion. However, detailed analysis revealed that, despite the higher exoergicity of the reaction, the rotational distribution of the OH following the reaction of O( 1 D2) with C3H8 was significantly cooler than that with cyclo-C3H6, especially in the vibrational ground state. This observation was interpreted as the effect of the flexibility of the insertion complex and faster intramolecular vibrational relaxation (IVR).

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Primary energy distribution in the products of the reaction F + HBr .fwdarw. HF(v') + Br

Cited by 37 publications

References 1 publication

Dynamical and stereodynamical studies of alkaline-earth atom–molecule reactions

Dynamical and stereodynamical studies of alkaline-earth atom–molecule reactions

A temperature dependence kinetic study of O(1D) + CH4: overall rate coefficient and product yields

Dynamics of OH Production in the Reaction of O(¹D₂) with Cyclopropane

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Primary energy distribution in the products of the reaction F + HBr .fwdarw. HF(v') + Br

Cited by 37 publications

References 1 publication

Dynamical and stereodynamical studies of alkaline-earth atom–molecule reactions

Dynamical and stereodynamical studies of alkaline-earth atom–molecule reactions

A temperature dependence kinetic study of O(1D) + CH4: overall rate coefficient and product yields

Dynamics of OH Production in the Reaction of O(1D2) with Cyclopropane

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Dynamics of OH Production in the Reaction of O(¹D₂) with Cyclopropane