NDLI: Ultrafast Dynamics of Nonequilibrium Electron Transfer in Photoinduced Redox Cycle: Solvent Mediation and Conformation Flexibility

Content Provider	PubMed Central
Author	Kao, Ya-ting Guo, Xunmin Yang, Yi Liu, Zheyun Hassanali, Ali Song, Qin-hua Wang, Lijuan Zhong, Dongping
Abstract	We report here our systematic characterization of a photoinduced electron-transfer (ET) redox cycle in a covalently linked donor-spacer-acceptor flexible system, consisting of N-acetyl-tryptophan methylester as electron donor and thymine as electron acceptor in three distinct solvents of water, acetonitrile and dioxane. With femtosecond resolution, we determined all the ET time scales, forward and backward, by following the complete reaction evolution from reactants, to intermediates and finally to products. Surprisingly, we observed two distinct ET dynamics in water, corresponding to a stacked configuration with ultrafast ET in 0.7 ps and back ET in 4.5 ps and a partially folded C-clamp conformation with ET in 322 ps but back ET in 17 ps. In acetonitrile and dioxane, only the C-clamp conformations were observed with ET in 470 and 1068 ps and back ET in 110 and 94 ps, respectively. These relatively slow ET dynamics in hundreds of picoseconds all showed significant conformation heterogeneity and followed a stretched decay behavior. With both forward and back ET rates determined, we derived solvent reorganization energies and coupling constants. Significantly, we found that solvent molecules intercalated in the cleft of the C-clamp structure mediate electron transfer with a tunneling parameter (β) of 1.0–1.4 Å−1 and the high-frequency vibration modes in the product(s) couple with the back ET process, leading to the ultrafast back ET dynamics in tens of picoseconds. These findings provide mechanistic insights of nonequilibrium ET dynamics modulated by conformation flexibility, mediated by unique solvent configuration, and accelerated by vibrational coupling.
Related Links	http://dx.doi.org/10.1021/jp304518f
Ending Page	9140
Page Count	11
Starting Page	9130
File Format	PDF
ISSN	15206106
e-ISSN	15205207
Journal	The journal of physical chemistry. B
Issue Number	30
Volume Number	116
Language	English
Publisher Date	2012-08-02
Access Restriction	Open
Subject Keyword	Physical and Theoretical Chemistry Materials Chemistry Surfaces, Coatings and Films Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Surfaces, Coatings and Films Materials Chemistry Medicine Physical and Theoretical Chemistry

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

Ultrafast Dynamics of Nonequilibrium Electron Transfer in Photoinduced Redox Cycle: Solvent Mediation and Conformation Flexibility

Ultrafast dynamics of nonequilibrium electron transfer in photoinduced redox cycle: solvent mediation and conformation flexibility.

Photoinduced Electron Transfer in Folic Acid Investigated by Ultrafast Infrared Spectroscopy

Role of Solvent Dynamics in Ultrafast Photoinduced Proton-Coupled Electron Transfer Reactions in Solution

Direct Observation and Control of Ultrafast Photoinduced Twisted Intramolecular Charge Transfer (TICT) in Triphenyl-Methane Dyes

Studies of Photoinduced Electron Transfer (PET) and Energy Migration in a Conjugated Polymer System for Fluorescence “Turn-on” Chemosensor Applications

Interfacial Bond-Breaking Electron Transfer in MixedWater–Ethylene Glycol Solutions: Reorganization Energy andInterplay between Different Solvent Modes

Surface Assisted Transient Displacement Charge Technique. I. Photoinduced Charge Transfer in Self-assembled Monolayers

Ultrafast Bimolecular Electron Transfer Dynamics in Micellar Media

Ultrafast Dynamics of Nonequilibrium Electron Transfer in Photoinduced Redox Cycle: Solvent Mediation and Conformation Flexibility

Similar Documents

Ultrafast Dynamics of Nonequilibrium Electron Transfer in Photoinduced Redox Cycle: Solvent Mediation and Conformation Flexibility

Ultrafast dynamics of nonequilibrium electron transfer in photoinduced redox cycle: solvent mediation and conformation flexibility.

Photoinduced Electron Transfer in Folic Acid Investigated by Ultrafast Infrared Spectroscopy

Role of Solvent Dynamics in Ultrafast Photoinduced Proton-Coupled Electron Transfer Reactions in Solution

Direct Observation and Control of Ultrafast Photoinduced Twisted Intramolecular Charge Transfer (TICT) in Triphenyl-Methane Dyes

Studies of Photoinduced Electron Transfer (PET) and Energy Migration in a Conjugated Polymer System for Fluorescence “Turn-on” Chemosensor Applications

Interfacial Bond-Breaking Electron Transfer in MixedWater–Ethylene Glycol Solutions: Reorganization Energy andInterplay between Different Solvent Modes

Surface Assisted Transient Displacement Charge Technique. I. Photoinduced Charge Transfer in Self-assembled Monolayers

Ultrafast Bimolecular Electron Transfer Dynamics in Micellar Media

Ultrafast Dynamics of Nonequilibrium Electron Transfer in Photoinduced Redox Cycle: Solvent Mediation and Conformation Flexibility