Solvent-dependent structure of molecular iodine probed by picosecond X-ray solution scattering

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The effect of solute-solvent interaction on molecular structure and reaction dynamics has been a target of intense studies in solution-phase chemistry, but it is often challenging to characterize the subtle effect of solute-solvent interaction even for the simplest diatomic molecules. Since the I-2 molecule has only one structural parameter and exhibits solvatochromism, it is a good model system for investigating the solvent dependence of the solute structure. By using X-rays as a probe, time-resolved X-ray liquidography (TRXL) can directly elucidate the structures of reacting molecules in solution and can thus determine the solvent-dependent structural change with atomic resolution. Here, by applying TRXL, we characterized the molecular structure of I-2 in methanol and cyclohexane with sub-angstrom accuracy. Specifically, we found that the I-I bond length of I-2 is longer in the polar solvent (methanol) by similar to 0.2 angstrom than in nonpolar solvents (cyclohexane and CCl4). Density functional theory (DFT) using 22 explicit methanol molecules well reproduces the longer I-I bond of molecular iodine in methanol and reveals that the larger bond length originates frompartial negative charge filled in an antibonding sigma* orbital through solvent-to-solute charge transfer.
Publisher
ROYAL SOC CHEMISTRY
Issue Date
2015
Language
English
Article Type
Article
Keywords

CHARGE-TRANSFER COMPLEXES; COMPUTER-SIMULATION; DYNAMICS; SPECTROSCOPY; STATE; TRANSITION; I-3(-); WATER

Citation

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.17, no.14, pp.8633 - 8637

ISSN
1463-9076
DOI
10.1039/c5cp00536a
URI
http://hdl.handle.net/10203/251200
Appears in Collection
CH-Journal Papers(저널논문)
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