Concerted Electron-Nuclear Motion in Proton-Coupled Electron Transfer-Driven Grotthuss-Type Proton Translocation.
Concerted Electron-Nuclear Motion in Proton-Coupled Electron Transfer-Driven Grotthuss-Type Proton Translocation.
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DOI：
10.1021/acs.jpclett.2c00585
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发表时间：
2022-05-26
影响因子：
5.7
通讯作者：
Fleming, Graham R.
中科院分区：
文献类型：
--
作者：
Arsenault, Eric A.;Guerra, Walter D.;Shee, James;Cruz, Edgar A. Reyez;Yoneda, Yusuke;Wadsworth, Brian L.;Odella, Emmanuel;Urrutia, Maria N.;Kodis, Gerdenis;Moore, Gary F.;Head-Gordon, Martin;Moore, Ana L.;Moore, Thomas A.;Fleming, Graham R.
在仿生结构中研究了通过 Grotthuss 型机制的光诱导质子耦合电子转移和长程二质子传输。超快、非平衡动力学通过二维电子振动光谱并结合电化学和计算技术进行评估。通过实验确定了低频模式，并发现它可以促进双质子和电子转移，并得到最近对类似但简化（非光活性）系统的理论模拟的支持。激发频率峰值演化和中心线斜率动力学显示了强耦合核和电子自由度的直接证据，从中我们可以得出结论，双质子和电子转移过程是一致的（不确定性高达 24 fs）。从光激发 Franck-Condon 区域到 E2PT 状态的非平衡路径的特点是~110 fs 的时间尺度。这项研究和本文提出的工具构成了涉及电子和多个质子的热电荷转移过程的新窗口。
Photoinduced proton-coupled electron transfer and long-range two-proton transport via a Grotthuss-type mechanism are investigated in a biomimetic construct. The ultrafast, nonequilibrium dynamics are assessed via two-dimensional electronic vibrational spectroscopy, in concert with electrochemical and computational techniques. A low-frequency mode is identified experimentally and found to promote double proton and electron transfer, supported by recent theoretical simulations of a similar but abbreviated (non-photoactive) system. Excitation frequency peak evolution and center line slope dynamics show direct evidence of strongly coupled nuclear and electronic degrees of freedom, from which we can conclude that the double proton and electron transfer processes are concerted (up to an uncertainty of 24 fs). The nonequilibrium pathway from the photoexcited Franck–Condon region to the E2PT state is characterized by an ∼110 fs time scale. This study and the tools presented herein constitute a new window into hot charge transfer processes involving an electron and multiple protons.
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影响因子：
18.2
作者：
Goings JJ;Hammes-Schiffer S
通讯作者：
Hammes-Schiffer S
影响因子：
4.8
作者：
Nagao, Ryo;Ueoka-Nakanishi, Hanayo;Noguchi, Takumi
通讯作者：
Noguchi, Takumi
影响因子：
15
作者：
Odella, Emmanuel;Wadsworth, Brian L.;Moore, Ana L.
通讯作者：
Moore, Ana L.
影响因子：
16.6
作者：
Arsenault EA;Yoneda Y;Iwai M;Niyogi KK;Fleming GR
通讯作者：
Fleming GR
影响因子：
8.4
作者：
Odella E;Mora SJ;Wadsworth BL;Goings JJ;Gervaldo MA;Sereno LE;Groy TL;Gust D;Moore TA;Moore GF;Hammes-Schiffer S;Moore AL
通讯作者：
Moore AL