Dynamics of iodine geminate recombination in supercritical xenon solvent: Caging effect

Mirakhory, M.; Majumdar, A.; Ihme, M.; van Duin, A. C. T.

doi:10.1063/5.0302862

Title: Dynamics of iodine geminate recombination in supercritical xenon solvent: Caging effect

Journal Article · Wed Mar 04 00:00:00 UTC 2026 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0302862 · OSTI ID:3364822

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Pennsylvania State Univ., University Park, PA (United States)
Stanford Univ., CA (United States)

Understanding the dynamics of chemical reactions in solutions is vital, as their rates and kinetics are significantly affected by the solvent environment. Supercritical solvents offer extensive applications in chemical reactions by enabling the manipulation of the solution environment. Here, in this study, we investigate the geminate recombination of iodine in a supercritical xenon solvent by using ReaxFF-based molecular dynamics simulations. Our findings reveal that the highest iodine recombination rate occurs near supercritical conditions, while lower-pressure conditions lead to reduced collision rates and unstable recombination, and higher-pressure conditions hinder iodine diffusion, resulting in a lower recombination rate. Our analysis shows that the xenon local density at the time of recombination is at least 2.5 times higher than the global density, confirming the presence of xenon clusters surrounding the Iodine atoms. This observation is further supported by coordination number analysis, which confirms an elevated xenon local density during recombination. In addition, the correlation between the total energy of xenon atoms within a cluster and recombined iodine atoms underscores the kinetic energy transfer process, validating the occurrence of geminate recombination. The excess kinetic energy from the recombining iodine atoms is transferred to the surrounding xenon atoms. Our examination of geminate recombination demonstrates that iodine atoms confined within xenon clusters—whether through manual insertion of atoms or the fast dissociation of an iodine molecule within xenon clusters—are more likely to recombine as primary geminate recombination. However, extending the iodine molecule dissociation time allows iodine atoms to diffuse out of the cluster, and the recombination to shift toward secondary geminate recombination.

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Research Organization:: Stanford Univ., CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022222; SC0026165

OSTI ID:: 3364822

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 164; ISSN 1089-7690; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Dynamics of iodine geminate recombination in supercritical xenon solvent: Caging effect

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