Polaritonic chemistry has ushered in new avenues for controlling molecular dynamics. However, two key questions remain: (i) Can classical light sources elicit the same effects as certain quantum light sources on molecular systems? (ii) Can semiclassical treatments of light-matter interaction capture nontrivial quantum effects observed in molecular dynamics? This work presents a quantum-classical approach addressing issues of realizing cavity chemistry effects without actual cavities. It also highlights the limitations of the standard semiclassical light-matter interaction. It is demonstrated that classical light sources can mimic quantum effects up to the second order of light-matter interaction, provided that the mean-field contribution, symmetrized two-time correlation function, and the linear response function are the same in both situations. Numerical simulations show that the quantum-classical method aligns more closely with exact quantum molecular-only dynamics for quantum light states such as Fock states, superpositions of Fock states, and vacuum squeezed states than the conventional semiclassical approach.Polaritonic chemistry has ushered in new avenues for controlling molecular dynamics. However, two key questions remain: (i) Can classical light sources elicit the same effects as certain quantum light sources on molecular systems? (ii) Can semiclassical treatments of light-matter interaction capture nontrivial quantum effects observed in molecular dynamics? This work presents a quantum-classical approach addressing issues of realizing cavity chemistry effects without actual cavities. It also highlights the limitations of the standard semiclassical light-matter interaction. It is demonstrated that classical light sources can mimic quantum effects up to the second order of light-matter interaction, provided that the mean-field contribution, symmetrized two-time correlation function, and the linear response function are the same in both situations. Numerical simulations show that the quantum-classical method aligns more closely with exact quantum molecular-only dynamics for quantum light states such as Fock states, superpositions of Fock states, and vacuum squeezed states than the conventional semiclassical approach.

arXiv:2312.06815Dec 11, 20230 citations

Slow photons in the fast lane in chemistry

Jennifer I. L. Chen, Georg von Freymann, Sung Yeun Choi +2 more

A driving force in the rapidly developing field of photonic crystals has been the photonic bandgap, a range of energies where the propagation of light is completely forbidden. The photonic bandgap allows the design of photonic lattices that localize, guide and bend light at sub-micron length scales, providing opportunities for the creation of miniature optical devices and integrated optical circuits to help drive the revolution in photonics. A less well known attribute of photonic crystals is their theoretical ability to slow light to a velocity of zero. This phenomenon can be achieved at the high and low energy edges of photonic stopgaps where the photonic bands are flat and light exists as a standing wave commensurate with the photonic lattice and travels at a group velocity of zero, referred to as “slow photons” herein. It has been shown theoretically that the probability of harvesting slow photons scales inversely with their group velocity. This means that a number of well known photon driven processes and devices in chemistry and physics can be enhanced by capturing this unique property of slow photons. In this paper we will look at slow photons mainly through the eye of chemistry and highlight some recent developments in this exciting and emerging field that demonstrate the potential of slow photons in materials chemistry and nanochemistry.A driving force in the rapidly developing field of photonic crystals has been the photonic bandgap, a range of energies where the propagation of light is completely forbidden. The photonic bandgap allows the design of photonic lattices that localize, guide and bend light at sub-micron length scales, providing opportunities for the creation of miniature optical devices and integrated optical circuits to help drive the revolution in photonics. A less well known attribute of photonic crystals is their theoretical ability to slow light to a velocity of zero. This phenomenon can be achieved at the high and low energy edges of photonic stopgaps where the photonic bands are flat and light exists as a standing wave commensurate with the photonic lattice and travels at a group velocity of zero, referred to as “slow photons” herein. It has been shown theoretically that the probability of harvesting slow photons scales inversely with their group velocity. This means that a number of well known photon driven processes and devices in chemistry and physics can be enhanced by capturing this unique property of slow photons. In this paper we will look at slow photons mainly through the eye of chemistry and highlight some recent developments in this exciting and emerging field that demonstrate the potential of slow photons in materials chemistry and nanochemistry.

Journal of Materials ChemistrySep 21, 2007154 citations

Atoms and Light

Amit Goswami

Springer eBooksJan 1, 20010 citations

Light Atoms

Springer eBooksMay 16, 20060 citations

The maximum refractive index of an atomic crystal $\unicode{x2013}$ from quantum optics to quantum chemistry

Andreoli, Francesco, Bennet Windt, Stefano Grava +4 more

All known optical materials have an index of refraction of order unity. Despite the tremendous implications that an ultrahigh index could have for optical technologies, little research has been done on why the refractive index of materials is universally small, and whether this observation is fundamental. Here, we investigate the index of an ordered arrangement of atoms, as a function of atomic density. At dilute densities, this problem falls into the realm of quantum optics, where atoms do not interact with one another except via the scattering of light. On the other hand, when the lattice constant becomes comparable to the Bohr radius, the electronic orbitals begin to overlap, giving rise to quantum chemistry. We present a minimal model that allows for a unifying theory of index spanning these two regimes. A key aspect is the treatment of multiple light scattering, which can be highly non-perturbative over a large density range, and which is the reason that conventional theories of the index break down. In the quantum optics regime, we show that ideal light-matter interactions can have a single-mode nature, allowing for a purely real refractive index that grows with density as $(N/V)^{1/3}$ . At the onset of quantum chemistry, we show how two physical mechanisms (excited electron tunneling dynamics and the buildup of electronic density-density correlations) can open up inelastic or spatial multi-mode light scattering processes, which ultimately reduce the index back to order unity while introducing absorption. Around the onset of chemistry, our theory predicts that ultrahigh index ( $n\sim 30$ ), low-loss materials could in principle be allowed by the laws of nature.All known optical materials have an index of refraction of order unity. Despite the tremendous implications that an ultrahigh index could have for optical technologies, little research has been done on why the refractive index of materials is universally small, and whether this observation is fundamental. Here, we investigate the index of an ordered arrangement of atoms, as a function of atomic density. At dilute densities, this problem falls into the realm of quantum optics, where atoms do not interact with one another except via the scattering of light. On the other hand, when the lattice constant becomes comparable to the Bohr radius, the electronic orbitals begin to overlap, giving rise to quantum chemistry. We present a minimal model that allows for a unifying theory of index spanning these two regimes. A key aspect is the treatment of multiple light scattering, which can be highly non-perturbative over a large density range, and which is the reason that conventional theories of the index break down. In the quantum optics regime, we show that ideal light-matter interactions can have a single-mode nature, allowing for a purely real refractive index that grows with density as $(N/V)^{1/3}$. At the onset of quantum chemistry, we show how two physical mechanisms (excited electron tunneling dynamics and the buildup of electronic density-density correlations) can open up inelastic or spatial multi-mode light scattering processes, which ultimately reduce the index back to order unity while introducing absorption. Around the onset of chemistry, our theory predicts that ultrahigh index ($n\sim 30$), low-loss materials could in principle be allowed by the laws of nature.

arXiv:2303.10998Mar 20, 20230 citations

(N/V)^{1/3}

. At the onset of quantum chemistry, we show how two physical mechanisms (excited electron tunneling dynamics and the buildup of electronic density-density correlations) can open up inelastic or spatial multi-mode light scattering processes, which ultimately reduce the index back to order unity while introducing absorption. Around the onset of chemistry, our theory predicts that ultrahigh index (

n\sim 30

), low-loss materials could in principle be allowed by the laws of nature.