Ground state chemistry under vibrational strong coupling: dependence of thermodynamic parameters on the Rabi splitting energy
Ground state chemistry under vibrational strong coupling: dependence of thermodynamic parameters on the Rabi splitting energy
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DOI：
10.1515/nanoph-2019-0340
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发表时间：
2019-11
期刊：
影响因子：
7.5
通讯作者：
Anoop Thomas;Anjali Jayachandran;Lucas Lethuillier-Karl;Robrecht M. A. Vergauwe;Kalaivanan Nagarajan;É. Devaux;C. Genet;J. Moran;T. Ebbesen
中科院分区：
文献类型：
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作者：
Anoop Thomas;Anjali Jayachandran;Lucas Lethuillier-Karl;Robrecht M. A. Vergauwe;Kalaivanan Nagarajan;É. Devaux;C. Genet;J. Moran;T. Ebbesen
摘要 振动强耦合（VSC）目前正在成为一种控制化学动力学的工具。在这里，我们研究了由拉比分裂能 (ħΩR) 给出的强耦合强度对与模型分子 1-苯基-2-三甲基甲硅烷基乙炔的脱甲硅基反应过渡态相关的热力学参数的影响。在 VSC 下，由温度依赖性动力学研究确定的活化焓和熵随耦合强度呈非线性变化。非空腔反应的热力学参数没有表现出明显的变化，排除了 VSC 下观察到的变化除了增强的 ħΩR 之外的浓度影响。 VSC 下和非空腔下的总自由能变化之间的差异相对较小，可能是因为活化的焓和熵相互补偿。这项热力学研究使人们更深入地了解集体强耦合对过渡态的作用，从而导致动力学和支化比的改变。
Abstract Vibrational strong coupling (VSC) is currently emerging as a tool to control chemical dynamics. Here we study the impact of strong coupling strength, given by the Rabi splitting energy (ħΩR), on the thermodynamic parameters associated with the transition state of the desilylation reaction of the model molecule 1-phenyl-2-trimethylsilylacetylene. Under VSC, the enthalpy and entropy of activation determined from the temperature-dependent kinetic studies varied nonlinearly with the coupling strength. The thermodynamic parameters of the noncavity reaction did not show noticeable variation, ruling out concentration effects other than the enhanced ħΩR for the changes observed under VSC. The difference between the total free energy change under VSC and in noncavity was relatively smaller possibly because the enthalpy and entropy of activation compensate each other. This thermodynamic study gives more insight into the role of collective strong coupling on the transition state that leads to modified dynamics and branching ratios.