Abstract
The photochemical reaction pathways of CHBr3 in solution were unveiled using two complementary X-ray techniques, time-resolved X-ray solution scattering (TRXSS) and X-ray transient absorption spectroscopy, in a wide temporal range from 100 ps to tens of microseconds. By performing comparative measurements in protic (methanol) and aprotic (methylcyclohexane) solvents, we found that the reaction pathways depend significantly on the solvent properties. In methanol, the major photoproducts are CH3OCHBr2 and HBr generated by rapid solvolysis of iso-CHBr2-Br, an isomer of CHBr3. In contrast, in methylcyclohexane, iso-CHBr2-Br returns to CHBr3 without solvolysis. In both solvents, the formation of CHBr2 and Br is a competing reaction channel. From the structural analysis of TRXSS data, we determined the structures of key intermediate species, CH3OCHBr2 and iso-CHBr2-Br in methanol and methylcyclohexane, respectively, which are consistent with the structures from density functional theory calculations.
Highlights
An understanding of reaction mechanisms at atomic and electronic levels is one of the central themes in chemistry; many efforts have been devoted toward that goal with advances in chemical reaction dynamics
From the structural analysis of time-resolved X-ray solution scattering (TRXSS) data, we determined the structures of key intermediate species, CH3OCHBr2 and iso-CHBr2-Br in methanol and methylcyclohexane, respectively, which are consistent with the structures from density functional theory calculations
To determine the structure of iso-CHBr2-Br in solution, we studied the photochemistry of CHBr3 in methylcyclohexane using time-resolved X-ray liquidography (TRXL) and X-ray transient absorption (XTA)
Summary
An understanding of reaction mechanisms at atomic and electronic levels is one of the central themes in chemistry; many efforts have been devoted toward that goal with advances in chemical reaction dynamics.
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