化学
从头算
联轴节(管道)
分子
方向(向量空间)
微波腔
耦合强度
极化(电化学)
化学物理
放松(心理学)
空腔壁
分子物理学
计算化学
物理
材料科学
微波食品加热
凝聚态物理
量子力学
物理化学
几何学
复合材料
有机化学
社会心理学
冶金
数学
心理学
作者
Marcus D. Liebenthal,A. Eugene DePrince
摘要
Recent theoretical studies have explored how ultra-strong light–matter coupling can be used as a handle to control chemical transformations. Ab initio cavity quantum electrodynamics calculations demonstrate that large changes to reaction energies or barrier heights can be realized by coupling electronic degrees of freedom to vacuum fluctuations associated with an optical cavity mode, provided that large enough coupling strengths can be achieved. In many cases, the cavity effects display a pronounced orientational dependence. Here, we highlight the critical role that geometry relaxation can play in such studies. As an example, we consider a recent work [Pavošević et al., Nat. Commun. 14, 2766 (2023)] that explored the influence of an optical cavity on Diels–Alder cycloaddition reactions and reported large changes to reaction enthalpies and barrier heights, as well as the observation that changes in orientation can inhibit the reaction or select for one reaction product or another. Those calculations used fixed molecular geometries optimized in the absence of the cavity and fixed relative orientations of the molecules and the cavity mode polarization axis. Here, we show that when given a chance to relax in the presence of the cavity, the molecular species reorient in a way that eliminates the orientational dependence. Moreover, in this case, we find that qualitatively different conclusions regarding the impact of the cavity on the thermodynamics of the reaction can be drawn from calculations that consider relaxed vs unrelaxed molecular structures.
科研通智能强力驱动
Strongly Powered by AbleSci AI