Collectively-modified inter-molecular electron correlations: The connection of polaritonic chemistry and spin glass physics

TL;DR

This paper establishes a theoretical link between polaritonic chemistry and spin glass physics by mapping molecular electron interactions under strong coupling to a spin glass model, revealing new insights into chemical modifications and phase transitions.

Contribution

It introduces a novel theoretical framework connecting polaritonic chemistry with spin glass models, enabling the application of spin glass concepts to chemical systems under strong light-matter coupling.

Findings

Mapping of molecular electron correlations to the SSK spin glass model.

Prediction of instability in intermolecular electron correlations due to collective effects.

Qualitative agreement of model predictions with experimental observations.

Abstract

Polaritonic chemistry has garnered increasing attention in recent years due to pioneering experimental results, which show that site- and bond-selective chemistry at room temperature is achievable through strong collective coupling to field fluctuations in optical cavities. Despite these notable experimental strides, the underlying theoretical mechanisms remain unclear. In this focus review, we highlight a fundamental theoretical link between the seemingly unrelated fields of polaritonic chemistry and spin glasses, exploring its profound implications for the theoretical framework of polaritonic chemistry. Specifically, we present a mapping of the dressed many-molecules electronic-structure problem under collective vibrational strong coupling to the spherical Sherrington-Kirkpatrick (SSK) model of a spin glass. This mapping uncovers a collectively induced instability of the intermolecular electron correlations, which could provide the long sought-after seed for significant local chemical modifications in polaritonic chemistry. Overall, the qualitative predictions made from the SSK model (e.g., dispersion effects, phase transitions, differently modified bulk and rare event properties, heating,...) agree well with available experimental observations. Our connection paves the way to incorporate, adjust and probe numerous spin glass concepts in polaritonic chemistry, such as modified fluctuation-dissipation relations, (non-equilibrium) aging dynamics, time-reversal symmetry breaking or stochastic resonances. Ultimately, the connection also offers fresh insights into the applicability of spin glass theory beyond condensed matter systems suggesting novel theoretical directions such as spin glasses with explicitly time-dependent (random) interactions.