Terry Weatherly Connor K, Provazza Justin, Weiss Emily A, Tempelaar Roel
Department of Chemistry, Northwestern University, Evanston, IL, 60208-3113, USA.
Nat Commun. 2023 Aug 9;14(1):4804. doi: 10.1038/s41467-023-40400-z.
This work proposes a photophysical phenomenon whereby ultraviolet/visible (UV/vis) excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of excited state vibrational polaritons (ESVP) via UV/vis excitation only involve vibrational modes with both a non-zero FC activity and IR activity in the excited state. Density functional theory calculations are used to identify 1-Pyreneacetic acid as a molecule with this property and the dynamics of ESVP are modeled. Overall, this work introduces an avenue of polariton chemistry where excited state dynamics are influenced by the formation of vibrational polaritons. Along with this, the UV/vis-to-IR photonic down conversion is potentially useful in both sensing excited state vibrations and quantum transduction schemes.
这项工作提出了一种光物理现象，即涉及弗兰克-康登（FC）活性振动的分子的紫外/可见（UV/vis）激发通过与光学腔的强耦合产生红外（IR）发射。由此产生的紫外/可见到红外的光子下转换过程由电子激发态势中的振动极化激元介导。结果表明，通过紫外/可见激发形成激发态振动极化激元（ESVP）仅涉及在激发态中具有非零FC活性和红外活性的振动模式。密度泛函理论计算用于确定1-芘乙酸为具有此性质的分子，并对ESVP的动力学进行建模。总体而言，这项工作引入了一条极化激元化学途径，其中激发态动力学受振动极化激元形成的影响。与此同时，紫外/可见到红外的光子下转换在传感激发态振动和量子转导方案中都可能有用。
