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Sub-nanosecond secondary geminate recombination in mercury halides HgX2 (X = I, Br) investigated by time-resolved x-ray scattering

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Title
Sub-nanosecond secondary geminate recombination in mercury halides HgX2 (X = I, Br) investigated by time-resolved x-ray scattering
Author(s)
Denis Leshchev; Dmitry Khakhulin; Gemma Newby; Hosung Ki; Hyotcherl Ihee; Michael Wulff
Publication Date
2019-08
Journal
JOURNAL OF CHEMICAL PHYSICS, v.151, no.5, pp.054310 -
Publisher
AMER INST PHYSICS
Abstract
© 2019 Author(s).In this work, we present a detailed investigation on the recombination dynamics of mercury halides HgX2 (X = I, Br) in acetonitrile solution after UV-induced photodissociation. The study is performed by combining time-resolved wide-angle x-ray scattering (TRWAXS) and optical transient absorption spectroscopy. Up to 68% of the UV (266 nm) photodissociated HgX and X radicals that escape the solvent cage surrounding parent HgX2 recombine within a nanosecond after photodissociation. In contrast to classical primary geminate recombination, occurring on much faster time scales, we interpret the sub-nanosecond recombination channel as secondary geminate recombination (SGR), also referred to as diffusion-limited geminate recombination. The family of triatomic mercury halides therefore represents an important class of molecules to study chemical mechanisms of solvent-dependent SGR by TRWAXS. The methodology described here allows for direct mapping of the time-dependent inter-radical distance distribution function, a critical parameter for the assessment of the SGR dynamics in solution phase and solvation in general
URI
https://pr.ibs.re.kr/handle/8788114/6286
ISSN
0021-9606
Appears in Collections:
Center for Nanomaterials and Chemical Reactions(나노물질 및 화학반응 연구단) > Journal Papers (저널논문)
Files in This Item:
J. Chem. Phys. 151, 054310 (2019).pdfDownload

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