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- W2092080377 abstract "The chloroform anion in liquid methylcyclohexane (MCH) fragments during the time scale of geminate ion recombination (143 K ≤ T ≤ 193 K). Its lifetime can only be determined if the geminate ion kinetics can be calculated. The t-0.6 semiempirical law is used. Because CHCl3 quenches M+*, the precursor of the solvent radical cation MCH+, much less effectively than N2O, the fragmentation of M+* to produce the methylcyclohexene cation (MCHene+) has to be considered by theory. The t-0.6 simulation therefore was modified to include the two parallel reactions of the M+* decay, which are forming mixed ion pairs (MCHene+, MCH+/X-). It is found that mixed pairs are still describable by the t-0.6 linearity, yet the mobility factor δ (slope of t-0.6) is now λ-dependent. Complete simulation of the ionic mechanism yields the following results: (1) The fragmentation rate constant for is k1(143 K) = (3.6 ± 0.3) × 106 s-1 with Eact = 4.6 ± 0.5 kJ/mol and logA = 8.2 ± 0.2. The lifetime of 280 ns is substantially larger than expected from gas phase data. (2) By applying the known Gfi values to the free ion spectra at 143 K, 153 K, and 173 K, the absorption coefficients of the band were determined and a Lorentzian line shape fitted: λmax = 470 nm, εmax = 1900 ± 30 M-1 s-1 and a width of hwhm = 28 ± 2 nm. (3) Assuming that the M+* fragmentation (kfrag) and the natural relaxation to MCH+ (k0) are the same as in N2O-saturated MCH, the quenching rate constant at 143 K may be derived: k2(M+* + CHCl3 → MCH+) = (7.7 ± 2.6) × 106 M-1 s-1. Quenching by CHCl3 therefore is about four times slower than by N2O; the yield of the olefinic cation (MCHene+) is strongly increased relative to the MCH+ yield. Furthermore, the ratio quenching/fragmentation with chloroform as solute is found to increase with temperature, suggesting that fragmentation at room temperature might have much less importance." @default.
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- W2092080377 date "1999-06-11" @default.
- W2092080377 modified "2023-10-18" @default.
- W2092080377 title "Chloroform Anion Fragmentation in Liquid Methylcyclohexane: <i>t</i><sup>-0.6</sup> Simulation of the Geminate Ion Kinetics" @default.
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- W2092080377 doi "https://doi.org/10.1021/jp984760w" @default.
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