Photolysis of Br 2 in CCl 4 studied by time-resolved X-ray scattering

Qingyu Kong, Jae Hyuk Lee, Manuela Lo Russo, Tae Kyu Kim, MacIej Lorenc, Marco Cammarata, Savo Bratos, Thomas Buslaps, Veijo Honkimaki, Hyotcherl Ihee, Michael Wulff

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

A time-resolved X-ray solution scattering study of bromine molecules in CCl4 is presented as an example of how to track atomic motions in a simple chemical reaction. The structures of the photoproducts are tracked during the recombination process, geminate and non-geminate, from 100 ps to 10 s after dissociation. The relaxation of hot Br2 * molecules heats the solvent. At early times, from 0.1 to 10 ns, an adiabatic temperature rise is observed, which leads to a pressure gradient that forces the sample to expand. The expansion starts after about 10 ns with the laser beam sizes used here. When thermal artefacts are removed by suitable scaling of the transient solvent response, the excited-state solute structures can be obtained with high fidelity. The analysis shows that 30% of Br2 * molecules recombine directly along the X potential, 60% are trapped in the A/A′ state with a lifetime of 5.5 ns, and 10% recombine non-geminately via diffusive motion in about 25 ns. The Br - Br distance distribution in the A/A′ state peaks at 3.0 Å.

Original languageEnglish
Pages (from-to)252-260
Number of pages9
JournalActa Crystallographica Section A: Foundations of Crystallography
Volume66
Issue number2
DOIs
Publication statusPublished - 2010 Mar 1

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Photolysis
X ray scattering
photolysis
Hot Temperature
X-Rays
Bromine
Molecules
scattering
Artifacts
Genetic Recombination
molecules
Lasers
x rays
bromine
Pressure gradient
pressure gradients
Excited states
Pressure
Temperature
Laser beams

All Science Journal Classification (ASJC) codes

  • Structural Biology

Cite this

Kong, Qingyu ; Lee, Jae Hyuk ; Lo Russo, Manuela ; Kim, Tae Kyu ; Lorenc, MacIej ; Cammarata, Marco ; Bratos, Savo ; Buslaps, Thomas ; Honkimaki, Veijo ; Ihee, Hyotcherl ; Wulff, Michael. / Photolysis of Br 2 in CCl 4 studied by time-resolved X-ray scattering In: Acta Crystallographica Section A: Foundations of Crystallography. 2010 ; Vol. 66, No. 2. pp. 252-260.
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Kong, Q, Lee, JH, Lo Russo, M, Kim, TK, Lorenc, M, Cammarata, M, Bratos, S, Buslaps, T, Honkimaki, V, Ihee, H & Wulff, M 2010, ' Photolysis of Br 2 in CCl 4 studied by time-resolved X-ray scattering ', Acta Crystallographica Section A: Foundations of Crystallography, vol. 66, no. 2, pp. 252-260. https://doi.org/10.1107/S0108767309054993

Photolysis of Br 2 in CCl 4 studied by time-resolved X-ray scattering . / Kong, Qingyu; Lee, Jae Hyuk; Lo Russo, Manuela; Kim, Tae Kyu; Lorenc, MacIej; Cammarata, Marco; Bratos, Savo; Buslaps, Thomas; Honkimaki, Veijo; Ihee, Hyotcherl; Wulff, Michael.

In: Acta Crystallographica Section A: Foundations of Crystallography, Vol. 66, No. 2, 01.03.2010, p. 252-260.

Research output: Contribution to journalArticle

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AU - Cammarata, Marco

AU - Bratos, Savo

AU - Buslaps, Thomas

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AU - Ihee, Hyotcherl

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N2 - A time-resolved X-ray solution scattering study of bromine molecules in CCl4 is presented as an example of how to track atomic motions in a simple chemical reaction. The structures of the photoproducts are tracked during the recombination process, geminate and non-geminate, from 100 ps to 10 s after dissociation. The relaxation of hot Br2 * molecules heats the solvent. At early times, from 0.1 to 10 ns, an adiabatic temperature rise is observed, which leads to a pressure gradient that forces the sample to expand. The expansion starts after about 10 ns with the laser beam sizes used here. When thermal artefacts are removed by suitable scaling of the transient solvent response, the excited-state solute structures can be obtained with high fidelity. The analysis shows that 30% of Br2 * molecules recombine directly along the X potential, 60% are trapped in the A/A′ state with a lifetime of 5.5 ns, and 10% recombine non-geminately via diffusive motion in about 25 ns. The Br - Br distance distribution in the A/A′ state peaks at 3.0 Å.

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