Department of Chemistry and Cherry Emerson Center for Scientific Computation, Emory University, 201 Dowman Dr., Atlanta, Georgia 30322, USA.
J Chem Phys. 2023 Jul 21;159(3). doi: 10.1063/5.0156008.
Chemical reactions and energy transport phenomena have been experimentally reported to be significantly affected by strong light-matter interactions and vibrational polariton formation. These quasiparticles exhibit nontrivial transport phenomena due to the long-range correlations induced by the photonic system and elastic and inelastic scattering processes driven by matter disorder. In this article, we employ the Ioffe-Regel criterion to obtain vibrational polariton mobility edges and to identify distinct regimes of delocalization and transport under variable experimental conditions of light-matter detuning, disorder, and interaction strength. Correlations between the obtained trends and recent observations of polariton effects on reactivity are discussed, and essential differences between transport phenomena in organic electronic exciton and vibrational polaritons are highlighted. Our transport diagrams show the rich diversity of transport phenomena under vibrational strong coupling and indicate that macroscopic delocalization is favored at negative detuning and large light-matter interaction strength. We also find the surprising feature that, despite the presence of dephasing-induced inelastic scattering processes, macroscopic lower polariton delocalization and wave transport are expected to persist experimentally, even in modes with small photonic weight.
化学反應和能量傳輸現象已被實驗報告受到強光物質相互作用和振動等離子體形成的顯著影響。這些准粒子由於光子系統誘導的長程相關和物質混亂驅動的彈性和非彈性散射過程，表現出非平凡的傳輸現象。在本文中，我們利用 Ioffe-Regel 判據來獲得振動等離子體遷移率邊界，並在不同的光物質失諧、混亂和相互作用強度的實驗條件下，確定去局域化和傳輸的不同模式。討論了所得趨勢與最近觀察到的等離子體效應對反應性的相關性，並強調了有機電子激子和振動等離子體中傳輸現象的基本區別。我們的傳輸圖表明在振動強耦合下傳輸現象的多樣性，並表明在負失諧和大的光物質相互作用強度下，宏觀去局域化更有利。我們還發現了一個令人驚訝的特徵，即使存在相消干擾引起的非彈性散射過程，宏觀下等離子體的去局域化和波動傳輸也有望在實驗中持續存在，即使在光子權重較小的模式中也是如此。
