Excited Hydrogen Halides

V.Lebed and E.E.Nikitin, Deactivation of rotationally excited hydrogen halide molecules, Doklady Akad.Nauk SSSR 224, 373 (1975)... 

The reactions of excited hydrogen halides are convenient to study because of the availability of hydrogen halide chemical lasers for excitation. The correlation between ground-state heats of reaction and vibration-ally induced reaction rate enhancement is striking for these processes (Table I). As expected, reaction enhancement is observed for all reactions except for those that are exothermic. In the case of reaction (2) the reaction rate is... 

Because they lend themselves to studies using both photochemical and chemical activation, bimolecular reactions of vibrationally excited hydrogen halides have been more throughly investigated than any other family of reactions. The rate constants in Table 1.3 have been obtained by the laser-induced vibrational fluorescence technique and correspond to the sum of rate constants for reactive and inelastic processes. The main problem is to establish the atomic concentrations accurately. This is usually accomplished by gas-phase titration in a discharge-flow system, although photolysis methods have also been employed. To find the ratio of reaction to non-reactlve relaxation, product concentrations have to be observed. This has been done in relatively few cases. Some systems have also been studied using the infrared chemiluminescence depletion technique (see Section 1.5.1). These experiments supply relative rate data for removal from several vibrational levels, and, in favorable cases, also provide some information about the rotational-state dependence of these rates. 

The availability of well-characterized pulsed hydrogen halide chemical lasers has permitted the application of these methods to a variety of chemical reactions which generate vibrationally excited hydrogen halide reaction products. As tunable infrared laser sources are being more extensively developed, these methods will undoubtedly be applied to a much larger class of reactions. 

The photoadditions of halogens, hydrogen halides, and alkylhalides to olefins have been extensively documented.<107) Photohalogenation reactions occur by absorption of light by the halogen, leading to excitation of a non-bonded p electron to an antibonding a excited level, followed by decomposition of the molecule into free radicals ... 

An alternative LIS scheme is one in which a vibrationally excited molecule reacts preferentially with another species. An example is the hydrogen halide/olefin addition reaction, DX + RiR2C = CH2 RiR2CXCH2D. The scheme involves sequential absorption of several quanta from a C02 laser near 5 p,m to selectively excite DX to a vibrational quantum number of 3 or more. Successful implementation would be expensive because of the highly corrosive nature of halogen acids. 

Comparison of molecular oxygen and hydrogen halide excitation... 

The initial step in the double-resonance scheme is the excitation of a local mode hydrogen stretch vibration localized in a hydrogen halide moiety. In principle, this can be done either at the fundamental or one of the overtones. With presently available Ti sapphire lasers and parametric oscillators (OPOs), it is possible to saturate fundamentals and first overtones, thus ensuring maximum population transfer. Second overtones cannot be pumped as efficiently, but offer enormous discrimination against background and can be used to shift frequencies out of the vacuum ultraviolet and into a more user-friendly part of the ultraviolet. Thus, first and second overtones are very attractive. 

Reactions within a van der Waals (vdW) complex of calcium with hydrogen halides (HC1 and HBr) lead to electronically excited calcium halides. These reactions have been quite extensively studied in full collisions of excited calcium beams (Brinckmann et al. 1980 Brinckmann and Telle 1977 Rettner and Zare 1981, 1982 Telle and Brinckmann 1990). The electronic excitation of the calcium atom results in a strong chemiluminescence under collisional conditions. The efficiency of this chemiluminescence depends upon the electronic state and the fine structure component, and the final product state is influenced by the preparation conditions of the collision. In the reaction Ca(4s4p1P1) + HC1, the direction of the polarization of the P orbital with respect to the collision relative velocity (pK or pff) has an effect on the branching ratio to the products CaCl, A2n or B2X+ (Rettner and Zare 1981, 1982). 

The photoreduction of 2- and 3-chloroanisole in alcoholic solvents has been studied and is considered to be best accounted for by invoking methoxyphenyl radicals which abstract hydrogen atoms from the solvent378.4-Chloroanisole probably reacts partly via a homolytic cleavage, but in view of the results of quenching and sensitization experiments, another pathway consists of electron transfer from the solvent (ROH) to excited aryl halide, followed by dissociation of the radical anion into chloride ion and aryl radical. 

V-V exchange between two hydrogen halides has been observed by Chen, Stephenson, and Moore [218] utilizing laser-excited vibrational fluorescence. The vibration-vibration transfer rate for HC1-HI collisions was determined by measurement of the exponential decay of HC1 Av = 1 fluorescence following excitation by an HC1 laser pulse. The relaxation time for the process... 

The use of laser-induced fluorescence as a molecular beam detector for the measurement of internal state distributions of reaction products is presented and applied to the reactions of barium with the hydrogen halides. It is found that most of the reaction exoergicity appears as translational energy of the products and that the total reactive cross section is positively correlated with the average fraction of the exoergicity appearing as vibrational excitation. 

There has been considerable interest in the elimination of hydrogen halides from halogenated hydrocarbon molecules and radicals which have been vibration-ally excited by chemical activation, by photochemical methods or by shock-tube techniques. Studies on fluorinated species have been reported by Trotman-Dickenson et a/.7 3.839-84i,846.908,909 by Pritchard et fl/.747,748.905.919.920 ... 

The gas-phase photochemistry of haiogenated ethenes has been studied in the UV and VUV [60, 61], as well as in the infrared, using multiple-photon-absorption excitation with powerful CO2 laser sources [62-66]. Also, sensitized decompositions, for example using electronically excited Hg( P) atoms, have also been reported [67-69]. The net gas-phase photochemistry of these systems usually involves hydrogen halide elimination via three-and/or four-center transition states, with some evidence for simple bond fission producing halogen atoms in the case of Hgf Pj) photosensitization [70]. 

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