Kinetics and mechanism of intramolecular electron transfer in solution

Dan Huppert*, Hannah Kanety, Edward M. Kosower

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The picosecond pulse generated S1,np state of 6-N-4-methylphenylamino-2-naphthalenesulphonic acid NN-dimethylamide (TNSDMA) decays by intramolecular electron transfer (i.e.t) faster than the appearance of the product, an equilibrium mixture of the charge-transfer, S1,ct, and S1,np states (temperature-independent ratio of 4-5), which decays at ca. 0.1 of the rate for the S1,np state. In propan-1-ol, rates of "fast" i.e.t. processes vary with solvent cluster motion (1/τ1, lowest dielectric relaxation rate) over a wide range of temperatures with log k linear in 2/3 log (1/η). Up to ca. -15°C, "slow" i.e.t. processes probably vary in the same way, but at higher temperatures they are controlled by local group motion (1/τ2, second lowest dielectric relaxation rate). A molecular model for the S 1,ct -state-methanol complex is presented.

Original languageEnglish
Pages (from-to)161-175
Number of pages15
JournalFaraday Discussions of the Chemical Society
Volume74
DOIs
StatePublished - 1982

Funding

FundersFunder number
United States-Israel Binational Science Foundation

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