Počet záznamů: 1
Excited-State Diproton Transfer in [2,2’-Bipyridyl]-3,3’-diol: the Mechanism Is Sequential, Not Concerted
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SYSNO ASEP 0329453 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Excited-State Diproton Transfer in [2,2’-Bipyridyl]-3,3’-diol: the Mechanism Is Sequential, Not Concerted Tvůrce(i) Plasser, F. (AT)
Barbatti, M. (AT)
Aquino, A. J. A. (AT)
Lischka, Hans (UOCHB-X)Celkový počet autorů 4 Zdroj.dok. Journal of Physical Chemistry A. - : American Chemical Society - ISSN 1089-5639
Roč. 113, č. 30 (2009), s. 8490-8499Poč.str. 10 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova excited-state diproton transfer ; on-the-fly dynamics simulations ; sequential and concerted mechanisms Vědní obor RIV CF - Fyzikální chemie a teoretická chemie CEP LC512 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy CEZ AV0Z40550506 - UOCHB-X (2005-2011) UT WOS 000268230200006 DOI 10.1021/jp9032172 Anotace The excited-state mono- and diproton transfer has been investigated in the S1 state RI-CC2 and TDDFT methods. These calculations show that the concerted diproton transfer in S1 proceeds along a ridge thus making this process unlikely. On-the-fly dynamics simulations performed at the RI-CC2 level confirm this picture. The present results shed new light on the interpretation of the experimental results. The simulations show that what has been experimentally determined as concerted transfer is in fact a combination of two sequential proton transfers separated by a small delay below the present experimental resolution. Both the forward and reverse reactions of a mono-/diketo equilibrium were found within the 300 fs period. Environmental effects will lead to a substantial cooling of the initially hot molecule and a concomitant decrease in the monoketo/diketo conversion rates, which will result in the experimentally observed overall time scale of 10 ps for the second proton transfer step. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Viktorie Chládková, Tel.: 232 002 434 Rok sběru 2010
Počet záznamů: 1