ISIS and USIAS, University of Strasbourg and CNRS , 8 allée Monge, 67000 Strasbourg, France.
Acc Chem Res. 2016 Nov 15;49(11):2403-2412. doi: 10.1021/acs.accounts.6b00295. Epub 2016 Oct 25.
The notion that light and matter states can be hybridized the way s and p orbitals are mixed is a concept that is not familiar to most chemists and material scientists. Yet it has much potential for molecular and material sciences that is just beginning to be explored. For instance, it has already been demonstrated that the rate and yield of chemical reactions can be modified and that the conductivity of organic semiconductors and nonradiative energy transfer can be enhanced through the hybridization of electronic transitions. The hybridization is not limited to electronic transitions; it can be applied for instance to vibrational transitions to selectively perturb a given bond, opening new possibilities to change the chemical reactivity landscape and to use it as a tool in (bio)molecular science and spectroscopy. Such results are not only the consequence of the new eigenstates and energies generated by the hybridization. The hybrid light-matter states also have unusual properties: they can be delocalized over a very large number of molecules (up to ca. 10), and they become dispersive or momentum-sensitive. Importantly, the hybridization occurs even in the absence of light because it is the zero-point energies of the molecular and optical transitions that generate the new light-matter states. The present work is not a review but rather an Account from the author's point of view that first introduces the reader to the underlying concepts and details of the features of hybrid light-matter states. It is shown that light-matter hybridization is quite easy to achieve: all that is needed is to place molecules or a material in a resonant optical cavity (e.g., between two parallel mirrors) under the right conditions. For vibrational strong coupling, microfluidic IR cells can be used to study the consequences for chemistry in the liquid phase. Examples of modified properties are given to demonstrate the full potential for the molecular and material sciences. Finally an outlook of future directions for this emerging subject is given.
光与物质状态可以像 s 和 p 轨道那样混合的概念,对于大多数化学家和材料科学家来说并不熟悉。然而,它在分子和材料科学中有很大的潜力,目前才刚刚开始探索。例如,已经证明可以通过电子跃迁的杂化来修饰化学反应的速率和产率,并且可以增强有机半导体和非辐射能量转移的电导率。这种杂化不仅限于电子跃迁;例如,可以应用于振动跃迁,以选择性地扰动给定的键,为改变化学反应性景观开辟新的可能性,并将其用作(生物)分子科学和光谱学中的工具。这些结果不仅是杂化产生的新本征态和能量的结果。杂化光物质态还具有不寻常的性质:它们可以在非常多的分子(高达约 10 个)上离域,并且变得色散或动量敏感。重要的是,即使没有光,杂化也会发生,因为正是分子和光学跃迁的零点能产生了新的光物质态。本工作不是一篇综述,而是作者观点的叙述,旨在首先向读者介绍杂化光物质态的基本概念和特征细节。结果表明,光物质杂化非常容易实现:只需要将分子或材料置于适当条件下的共振光学腔中(例如,在两个平行反射镜之间)。对于振动强耦合,可以使用微流控 IR 池来研究液相中化学的后果。给出了改性性质的示例,以展示其在分子和材料科学中的全部潜力。最后,给出了这个新兴主题未来发展方向的展望。