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DOI | 10.1126/science.aaw4675 |
PHYSICAL CHEMISTRY Concerted proton-electron transfer reactions in the Marcus inverted region | |
Parada, Giovanny A.1; Goldsmith, Zachary K.1; Kolmar, Scott1; Rimgard, Belinda Pettersson2; Mercado, Brandon Q.1; Hammarstrom, Leif2; Hammes-Schiffer, Sharon1; Mayer, James M.1 | |
2019-05-03 | |
发表期刊 | SCIENCE |
ISSN | 0036-8075 |
EISSN | 1095-9203 |
出版年 | 2019 |
卷号 | 364期号:6439页码:471-+ |
文章类型 | Article |
语种 | 英语 |
国家 | USA; Sweden |
英文摘要 | Electron transfer reactions slow down when they become very thermodynamically favorable, a counterintuitive interplay of kinetics and thermodynamics termed the inverted region in Marcus theory. Here we report inverted region behavior for proton-coupled electron transfer (PCET). Photochemical studies of anthracene-phenol-pyridine triads give rate constants for PCET charge recombination that are slower for the more thermodynamically favorable reactions. Photoexcitation forms an anthracene excited state that undergoes PCET to create a charge-separated state. The rate constants for return charge recombination show an inverted dependence on the driving force upon changing pyridine substituents and the solvent. Calculations using vibronically nonadiabatic PCET theory yield rate constants for simultaneous tunneling of the electron and proton that account for the results. |
领域 | 地球科学 ; 气候变化 ; 资源环境 |
收录类别 | SCI-E |
WOS记录号 | WOS:000466809600031 |
WOS关键词 | HYDROGEN-BONDED PHENOLS ; COUPLED ELECTRON ; TYROSINE OXIDATION ; BASIS-SETS ; DISTANCE ; QUANTUM ; THERMOCHEMISTRY ; DESIGN ; SERIES ; STATES |
WOS类目 | Multidisciplinary Sciences |
WOS研究方向 | Science & Technology - Other Topics |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/201343 |
专题 | 地球科学 资源环境科学 气候变化 |
作者单位 | 1.Yale Univ, Dept Chem, New Haven, CT 06520 USA; 2.Uppsala Univ, Dept Chem, Angstrom Lab, Uppsala, Sweden |
推荐引用方式 GB/T 7714 | Parada, Giovanny A.,Goldsmith, Zachary K.,Kolmar, Scott,et al. PHYSICAL CHEMISTRY Concerted proton-electron transfer reactions in the Marcus inverted region[J]. SCIENCE,2019,364(6439):471-+. |
APA | Parada, Giovanny A..,Goldsmith, Zachary K..,Kolmar, Scott.,Rimgard, Belinda Pettersson.,Mercado, Brandon Q..,...&Mayer, James M..(2019).PHYSICAL CHEMISTRY Concerted proton-electron transfer reactions in the Marcus inverted region.SCIENCE,364(6439),471-+. |
MLA | Parada, Giovanny A.,et al."PHYSICAL CHEMISTRY Concerted proton-electron transfer reactions in the Marcus inverted region".SCIENCE 364.6439(2019):471-+. |
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