NDLI: Isotope effect on ultrafast charge-transfer-to-solvent reaction from I<sup>−</sup> to water in aqueous NaI solution

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Novel and efficient templates for assembly of rotaxanes and catenanes

High-contrast Cu(i)-selective fluorescent probes based on synergistic electronic and conformational switching

Does supramolecular ordering influence exciton transport in conjugated systems? Insight from atomistic simulations

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Kinetics-driven high power Li-ion battery with a-Si/NiSi_x core-shell nanowire anodes

Isotope effect on ultrafast charge-transfer-to-solvent reaction from I⁻ to water in aqueous NaI solution

Cell-compatible, integrin-targeted cryptophane-¹²⁹Xe NMR biosensors

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Highly enantioselective palladium-catalyzed umpolung allylation of aldehydes

Spiro-2,2′-bichroman-based bisoxazoline (SPANbox) ligands for Zn^II-catalyzed enantioselective hydroxylation of β-keto esters and 1,3-diester

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Molecular coolers: The case for [Cu^II₅Gd^III₄]

The chemical vapor deposition of Cu₂ZnSnS₄ thin films

Chemical tuning of CO₂ sorption in robust nanoporous organic polymers

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Isotope effect on ultrafast charge-transfer-to-solvent reaction from I⁻ to water in aqueous NaI solution

Content Provider	Royal Society of Chemistry (RSC)
Author	Kurahashi, Naoya Shen, Huan Suzuki, Toshinori Suzuki, Yoshi-Ichi Sekiguchi, Kentaro Tang, Ying Mizuno, Tomoya
Copyright Year	2011
Abstract	A charge-transfer-to-solvent (CTTS) reaction from a photoexcited iodine atomic anion, I− (aq), in bulk water (H2O and D2O) was studied by time-resolved photoelectron spectroscopy using a liquid beam (microjet) of aqueous NaI solution. The 2P3/2 CTTS state of I− (aq) was excited by a 226 nm femtosecond laser pulse and the evolution of the nonstationary electronic state was probed using another ultraviolet femtosecond laser pulse. Global fitting of the observed time-dependent photoelectron kinetic energy distributions provided the time constants of individual reaction steps and the photoelectron spectra from the CTTS state, a contact pair, the solvent-separated state, and a hydrated electron. Most of the elementary reaction steps revealed a strong deuterium isotope effect, indicating coupling of the electron dynamics and the hydrogen atomic motion of solvent water. However, nondiffusive geminate recombination processes from the CTTS state and a contact pair were almost insensitive to deuteration. Consequently, geminate recombination processes from the CTTS state and a contact pair occurs more efficiently in D2O, because the response of water is decelerated in D2O. In contrast, the recombination process from the solvent-separated state in the final step of the CTTS reaction is less efficient in D2O, presumably due to the smaller zero point energy.
Starting Page	1094
Ending Page	1102
Page Count	9
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	2
Issue Number	6
Journal	Chemical Science
DOI	10.1039/c0sc00650e
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Femtosecond Deuterium Properties of water Isotope Hydrogen Carrier generation and recombination Ion Photoemission spectroscopy Ultraviolet Gemination Laser Elementary reaction Kinetic energy Solvent Iodine
Content Type	Text
Resource Type	Article
Subject	Chemistry

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