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Saeki A, Yamamoto N, Yoshida Y, et al. Geminate charge recombination in liquid alkane with concentrated CCl4: effects of CCl4 radical anion and narrowing of initial distribution of Cl-. J Phys Chem A. 2011;115(36):10166-73doi: 10.1021/jp205989r.
Saeki, A., Yamamoto, N., Yoshida, Y., & Kozawa, T. (2011). Geminate charge recombination in liquid alkane with concentrated CCl4: effects of CCl4 radical anion and narrowing of initial distribution of Cl-. The journal of physical chemistry. A, 115(36), 10166-73. https://doi.org/10.1021/jp205989r
Saeki, Akinori, et al. "Geminate charge recombination in liquid alkane with concentrated CCl4: effects of CCl4 radical anion and narrowing of initial distribution of Cl-." The journal of physical chemistry. A vol. 115,36 (2011): 10166-73. doi: https://doi.org/10.1021/jp205989r
Saeki A, Yamamoto N, Yoshida Y, Kozawa T. Geminate charge recombination in liquid alkane with concentrated CCl4: effects of CCl4 radical anion and narrowing of initial distribution of Cl-. J Phys Chem A. 2011 Sep 15;115(36):10166-73. doi: 10.1021/jp205989r. Epub 2011 Aug 24. PMID: 21863825.
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J Phys Chem A. 2011 Sep 15;115(36):10166-73. doi: 10.1021/jp205989r. Epub 2011 Aug 24.

Geminate charge recombination in liquid alkane with concentrated CCl4: effects of CCl4 radical anion and narrowing of initial distribution of Cl-.

The journal of physical chemistry. A

Akinori Saeki, Naoto Yamamoto, Yoichi Yoshida, Takahiro Kozawa

Affiliations

  1. The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan. [email protected]

PMID: 21863825 DOI: 10.1021/jp205989r

Abstract

Dynamics of radical cations and electrons in an admixture of a linear saturated hydrocarbon (n-dodecane) and halocarbon (carbon tetrachloride, CCl(4)) were investigated by picosecond electron beam pulse radiolysis. The decay of thermalized electrons (e(th)(-)) observed in infrared transient photoabsorption were simply accelerated by the addition of CCl(4), giving a high rate constant of 2.3 × 10(11) mol(-1) dm(3) s(-1). The decrease of the initial yield of e(th)(-) was quantified by C(37) (50 mmol), which is linked to the reaction of epithermal electrons (e(-)) with CCl(4). In contrast, the n-dodecane radical cation (RH(2)(•+)) monitored in the near-infrared indicated a convex-type dependence of the decay rate on CCl(4) concentration, although the initial yield of RH(2)(•+) remained almost constant up to a much higher CCl(4) concentration. The decay of RH(2)(•+) was analyzed by Monte Carlo simulations of geminate ion recombination with e(th)(-), chlorine anion (Cl(-)) formed via dissociative electron attachment, and CCl(4) radical anion. The results showed a good agreement with the experiments by considering two assumptions: (1) CCl(4) radical anion formed via e(th)(-) attachment and (2) narrowing of the initial distribution of Cl(-). The decrease in the initial yield of RH(2)(•+) at high CCl(4) concentration was well explained by immediate decomposition of CCl(4)(•+) to CCl(3)(+) and hole transfer from CCl(4)(•+) to adjacent RH(2) without diffusive motion of the reactants. Time-dependent density functional theory supported the spectroscopic assignment of intermediate species in the n-dodecane/CCl(4) system. The present results would be of help in understanding the electron capture reaction in multicomponent systems such as a chemically amplified resist in lithography.

© 2011 American Chemical Society

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