Significance Of Nuclear Quantum Effects In Hydrogen Bonded Molecular Chains
Significance Of Nuclear Quantum Effects In Hydrogen Bonded Molecular Chains
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DOI：
10.1021/acsnano.1c02572
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发表时间：
2021-05-25
期刊：
影响因子：
17.1
通讯作者：
Jelinek, Pavel
中科院分区：
文献类型：
--
作者：
Cahlik, Ales;Hellerstedt, Jack;Jelinek, Pavel
在氢键系统中，零点运动和隧穿等核量子效应可以通过潜在的物理和化学过程显着影响其材料性质。目前，直接观察核量子效应对氢键强度的影响以及由此产生的结构和电子影响仍然难以捉摸，这为更深入地了解利用其迷人的特性留下了机会。我们研究了一维醌二亚胺分子网络，它通过质子转移可能具有两种异构电子构型。在这里，我们证明，协同质子转移促进了离域的π电子沿着的分子链，这增强了分子单元之间的结合能，增加了链的机械稳定性，并产生独特的电子在间隙中的状态本地化在末端。这些研究结果表明，一类异构氢键分子系统的核量子效应在建立其化学和物理性质中发挥主导作用的识别。这一发现是通过协同质子隧穿控制低维分子材料的机械和电子性质的一个步骤。
In hydrogen-bonded systems, nuclear quantum effects such as zero-point motion and tunneling can significantly affect their material properties through underlying physical and chemical processes. Presently, direct observation of the influence of nuclear quantum effects on the strength of hydrogen bonds with resulting structural and electronic implications remains elusive, leaving opportunities for deeper understanding to harness their fascinating properties. We studied hydrogen-bonded one-dimensional quinonediimine molecular networks which may adopt two isomeric electronic configurations via proton transfer. Herein, we demonstrate that concerted proton transfer promotes a delocalization of pi-electrons along the molecular chain, which enhances the cohesive energy between molecular units, increasing the mechanical stability of the chain and giving rise to distinctive electronic in-gap states localized at the ends. These findings demonstrate the identification of a class of isomeric hydrogen-bonded molecular systems where nuclear quantum effects play a dominant role in establishing their chemical and physical properties. This identification is a step toward the control of mechanical and electronic properties of low-dimensional molecular materials via concerted proton tunneling.