Ground State Photochemistry

在强光-物质耦合中，局域表面等离子体共振(LSPR)与激子混合形成激子态，其能量与LSPR和激子的能量不同。因此，强烈的光-物质耦合使我们能够通过创建活化能降低的新反应途径来改变化学反应的能量格局。此外，激子是振子；因此，它们的基态具有非零能量。原则上，这些基态的性质可以通过协同控制分子激子和LSPR的性质来操纵，并用于操纵光化学反应的路径。在这个项目中，你将设计包含光反应分子的纳米结构等离子体组件，可以用来驱动全新类型的化学反应。等离子体纳米结构将通过将金属纳米颗粒附着在原子力显微镜探针上并使用干涉光刻来制造。通过对制造过程的控制，您将创建具有量身定制的属性的LSPR，该属性旨在与光活性分子相互作用。化学反应性将使用各种光谱和扫描探针显微镜方法来表征，并将与埃克塞特大学的研究人员合作，探索强烈的光-物质耦合对光化学反应能量格局的影响

In strong light-matter coupling, localised surface plasmon resonances (LSPRs) are mixed with excitons to form plexcitonic states, which have different energies to those of the separate LSPRs and excitons. Thus, strong light-matter coupling allows us to modify the energy landscapes for chemical reactions, by creating new reaction pathways with reduced activation energies. Moreover, plexcitons are oscillators; consequently, their ground states have non-zero energies. In principle, the properties of these ground states can be manipulated via synergistic control of the properties of the molecular excitons and the LSPR, and used to manipulate the pathways for photochemical reactions.In this project, you will design nanostructured plasmonic assemblies containing photoreactive molecules that can be used to drive entirely new kinds of chemical reaction. Plasmonic nanostructures will be fabricated by attaching metal nanoparticles to atomic force microscope probes and by using interferometric lithography. By control of the fabrication process you will create LSPRs with tailored properties designed to interact with photoactive molecules. Chemical reactivity will be characterised using a variety of spectroscopic and scanning probe microscopy methods, and in collaboration with researchers at Exeter University, the influence of strong light-matter coupling on the energy landscapes for photochemical reactions will be explored