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Solvent-dependent barrier heights of excited-state photoisomerization reactions

✍ Scribed by Eva Åkesson; Villy Sundström; Tomas Gillbro

Publisher: Elsevier Science
Year: 1985
Tongue: English
Weight: 772 KB
Volume: 121
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(85)87132-3

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✦ Synopsis

We have studred the ~sornenzarmn dynamrcs ol the dje dlethyl~e~ramethyllndocarbocynnlnr Iodide m n-alcohol solution by pxosecond absorphon speclroscopy. Ewdence for subslanhal changes of the barrier herght of Isomenzation wth rolvenr was found The acwalion energy of rsomenzallon at constant wscos~ty mcreases from = 5 kl mol-' m melhan LO 18 LJ mol-' in Ihe higher alcohols hexanol-dodecanol We discuss how this solvent-Induced vnrla~lon of ac~wauon energy rnus~ be accounrcd for when analyzing Isomenzanon rake dala m terms of Kramer+type thrones II 1s suggested that prewouslv reporkd non-Kramers behawour of measured wxnenzauon rates could be due 10 potcntlal barner shlfs

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