论文标题
极化化学:集体强耦合意味着强烈的局部修饰化学特性
Polaritonic Chemistry: Collective Strong Coupling Implies Strong Local Modification of Chemical Properties
论文作者
论文摘要
在过去的几年中,极化化学已成为一个快速发展的领域。许多实验观察结果表明,当物质与谐振腔模式(即混合光含量态出现时)时,化学性质可以从根本上改变,并且新颖的物理状态出现。到目前为止,解释和预测这些观察结果的理论方法要么仅限于现象学量子光学模型,该模型适用于描述集体极化效应,或者是针对小型系统尺寸的从头开始方法。以后的方法尤其引起争议,因为由于本质上较低的粒子数量,在计算上访问的粒子数量较低,因此无法明确包含集体效应。在这里,我们证明了一个可变大小的氮二聚体链,任何杂质都存在于集体耦合化学合奏(例如温度波动或反应过程)中的任何杂质都会诱导极化系统中的局部修饰。从中,我们推断出形成了一种新型的黑暗状态,由于环境共同耦合的环境,其局部化学特性在杂质上进行了大量修饰。我们的模拟将理论预测统一了量子光学模型(例如,集体暗状态和不同极性分支的形成)与单分子量子化学透视图,这取决于局部电荷的(量化)重新分布。此外,我们的发现表明,最近开发的QEDFT方法适合访问这些局部缩放的极化效应,它是更好地了解最新实验结果甚至设计新型实验方法的有用工具。所有这些都为许多新颖的发现和应用中的应用铺平了道路。
Polaritonic chemistry has become a rapidly developing field within the last few years. A multitude of experimental observations suggest that chemical properties can be fundamentally altered and novel physical states appear when matter is strongly coupled to resonant cavity modes, i.e. when hybrid light-matter states emerge. Up until now, theoretical approaches to explain and predict these observations were either limited to phenomenological quantum optical models, suited to describe collective polaritonic effects, or alternatively to ab initio approaches for small system sizes. The later methods were particularly controversial since collective effects could not be explicitly included due to the intrinsically low particle numbers, which are computationally accessible. Here, we demonstrate for a nitrogen dimer chain of variable size that any impurity present in a collectively coupled chemical ensemble (e.g. temperature fluctuations or reaction process) induces local modifications in the polaritonic system. From this we deduce that a novel dark state is formed, whose local chemical properties are modified considerably at the impurity due to the collectively coupled environment. Our simulations unify theoretical predictions from quantum optical models (e.g. formation of collective dark states and different polaritonic branches) with the single molecule quantum chemical perspective, which relies on the (quantized) redistribution of local charges. Moreover, our findings suggest that the recently developed QEDFT method is suitable to access these locally scaling polaritonic effects and it is a useful tool to better understand recent experimental results and to even design novel experimental approaches. All of which paves the way for many novel discoveries and applications in polaritonic chemistry.