Communication: oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH3 radical cations.
Communication: oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH3 radical cations.
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通讯：孤对电子之间的振荡电荷迁移持续存在，而与甘氨酸和 Gly-Gly-NH-CH3 自由基阳离子中的核运动没有显着的相互作用。
DOI：
10.1063/1.4879516
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
M. Robb
中科院分区：
文献类型：
--
作者：
M. Vacher;M. Bearpark;M. Robb
用Escherichfest方法研究了甘氨酸分子四种构象和Gly-Gly-NH-CH_3单一构象的电子-核耦合动力学。初始电子波包是本征态的叠加，对应于与羰基氧和胺氮相关的σ孤对电离。对于甘氨酸，振荡电荷迁移（当核被冻结）观察到的4个构象研究的周期范围从2至5 fs，这取决于孤对阳离子状态之间的能隙。当允许耦合核运动时（主要是NH 2部分反转），振荡几乎没有变化。对于Gly-Gly-NH-CH 3，可以观察到羰基氧和NH 2孤对电子之间的电荷迁移，其周期与甘氨酸本身相似，也不与核运动相互作用。这些模拟表明，孤对电子之间的电荷迁移可以独立于核运动而发生。
Coupled electron-nuclear dynamics has been studied, using the Ehrenfest method, for four conformations of the glycine molecule and a single conformation of Gly-Gly-NH-CH3. The initial electronic wavepacket was a superposition of eigenstates corresponding to ionization from the σ lone pairs associated with the carbonyl oxygens and the amine nitrogen. For glycine, oscillating charge migration (when the nuclei were frozen) was observed for the 4 conformers studied with periods ranging from 2 to 5 fs, depending on the energy gap between the lone pair cationic states. When coupled nuclear motion was allowed (which was mainly NH2 partial inversion), the oscillations hardly changed. For Gly-Gly-NH-CH3, charge migration between the carbonyl oxygens and the NH2 lone pair can be observed with a period similar to glycine itself, also without interaction with nuclear motion. These simulations suggest that charge migration between lone pairs can occur independently of the nuclear motion.
影响因子：
2.3
作者：
Kuleff, Alexander I.;Luennemann, Siegfried;Cederbaum, Lorenz S.
通讯作者：
Cederbaum, Lorenz S.