Abstract: Intermolecular bonds are weak compared to covalent bonds, but they are strong enough to influence the properties of large molecular systems. In this work, we investigate how strong light-matter coupling inside an optical cavity can modify intermolecular forces and illustrate the varying necessity of correlation in their description. The electromagnetic field inside the cavity can modulate the ground state properties of weakly bound complexes. Tuning the field polarization and cavity frequency, the interactions can be stabilized or destabilized, and electron densities, dipole moments, and polarizabilities can be altered. We demonstrate that electron-photon correlation is fundamental to describe intermolecular interactions in strong light-matter coupling. This work proposes optical cavities as a novel tool to manipulate and control ground state properties, solvent effects, and intermolecular interactions for molecules and materials.

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Topics: Intermolecular force (60%), Ground state (52%), Optical cavity (50%)

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17 results found

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Francisco J. Garcia-Vidal^{1}, Francisco J. Garcia-Vidal^{2}, Cristiano Ciuti^{3}, Thomas W. Ebbesen^{4}•Institutions (4)

Abstract: Over the past decade, there has been a surge of interest in the ability of hybrid light-matter states to control the properties of matter and chemical reactivity. Such hybrid states can be generated by simply placing a material in the spatially confined electromagnetic field of an optical resonator, such as that provided by two parallel mirrors. This occurs even in the dark because it is electromagnetic fluctuations of the cavity (the vacuum field) that strongly couple with the material. Experimental and theoretical studies have shown that the mere presence of these hybrid states can enhance properties such as transport, magnetism, and superconductivity and modify (bio)chemical reactivity. This emerging field is highly multidisciplinary, and much of its potential has yet to be explored.

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Topics: Electromagnetic field (52%), Field (physics) (51%)

18 Citations

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20 Sep 2021-

Abstract: A path to bridge the gap between ab initio materials calculations and the model Hamiltonians used to discover and develop scalable quantum systems is presented.

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Topics: Bridge (interpersonal) (58%)

12 Citations

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Abstract: Strong light-matter interaction in cavity environments has emerged as a promising approach to control chemical reactions in a non-intrusive and efficient manner. The underlying mechanism that distinguishes between steering, accelerating, or decelerating a chemical reaction has, however, remained unclear, hampering progress in this frontier area of research. In this work, we leverage a combination of first-principles techniques, foremost quantum-electrodynamical density functional theory, applied to the recent experimental realization by Thomas et al. [1] to unveil the microscopic mechanism behind the experimentally observed reduced reaction-rate under cavity induced resonant vibrational strong light-matter coupling. We find that the cavity mode functions as a mediator between different vibrational eigenmodes, transferring vibrational excitation and anharmonicity, correlating vibrations, and ultimately strengthening the chemical bond of interest. Importantly, the resonant feature observed in experiment, theoretically elusive so far, naturally arises in our investigations. Our theoretical predictions shine new light on cavity induced polaritonic chemistry, providing a crucial control strategy in state-of-the-art photocatalysis and energy conversion, pointing the way towards generalized quantum optical control of chemical processes.

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11 Citations

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Abstract: In the field of polaritonic chemistry, strong light-matter interactions are used to alter chemical reactions inside optical cavities. To understand these processes, the development of reliable theoretical models is essential. While traditional methods have to balance accuracy and system size, new developments in quantum computing offer a path for accurate calculations on currently available quantum devices. Here, we introduce the quantum electrodynamics unitary coupled cluster (QED-UCC) method combined with the Variational Quantum Eigensolver algorithm, as well as the quantum electrodynamics equation-of-motion (QED-EOM) method formulated in the qubit basis that allow accurate calculations of ground-state and excited-state properties of strongly coupled light-matter systems suitable for quantum computers. These methods show excellent agreement with the exact reference results and can outperform their traditional counterparts when strong electronic correlations become significant. This work sets the stage for future developments of polaritonic quantum chemistry methods suitable for both classical and quantum computers.

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Topics: Quantum computer (68%), Qubit (65%), Coupled cluster (56%) ... show more

5 Citations

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Abstract: We employ various quantum-mechanical approaches for studying the impact of electric fields on both nonretarded and retarded noncovalent interactions between atoms or molecules. To this end, we apply perturbative and non-perturbative methods within the frameworks of quantum mechanics (QM) as well as quantum electrodynamics (QED). In addition, to provide a transparent physical picture of the different types of resulting interactions, we employ a stochastic electrodynamic approach based on the zero-point fluctuating field. Atomic response properties are described via harmonic Drude oscillators - an efficient model system that permits an analytical solution and has been convincingly shown to yield accurate results when modeling non-retarded intermolecular interactions. The obtained intermolecular energy contributions are classified as field-induced (FI) electrostatics, FI polarization, and dispersion interactions. The interplay between these three types of interactions enables the manipulation of molecular dimer conformations by applying transversal or longitudinal electric fields along the intermolecular axis. Our framework combining four complementary theoretical approaches paves the way toward a systematic description and improved understanding of molecular interactions when molecules are subject to both external and vacuum fields.

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Topics: Field (physics) (54%), Intermolecular force (54%)

5 Citations

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65 results found

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Abstract: From a theory of Hohenberg and Kohn, approximation methods for treating an inhomogeneous system of interacting electrons are developed. These methods are exact for systems of slowly varying or high density. For the ground state, they lead to self-consistent equations analogous to the Hartree and Hartree-Fock equations, respectively. In these equations the exchange and correlation portions of the chemical potential of a uniform electron gas appear as additional effective potentials. (The exchange portion of our effective potential differs from that due to Slater by a factor of $\frac{2}{3}$.) Electronic systems at finite temperatures and in magnetic fields are also treated by similar methods. An appendix deals with a further correction for systems with short-wavelength density oscillations.

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Topics: Jellium (56%), Hartree–Fock method (55%), Thomas–Fermi model (55%) ... show more

42,177 Citations

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Abstract: This paper deals with the ground state of an interacting electron gas in an external potential $v(\mathrm{r})$. It is proved that there exists a universal functional of the density, $F[n(\mathrm{r})]$, independent of $v(\mathrm{r})$, such that the expression $E\ensuremath{\equiv}\ensuremath{\int}v(\mathrm{r})n(\mathrm{r})d\mathrm{r}+F[n(\mathrm{r})]$ has as its minimum value the correct ground-state energy associated with $v(\mathrm{r})$. The functional $F[n(\mathrm{r})]$ is then discussed for two situations: (1) $n(\mathrm{r})={n}_{0}+\stackrel{\ifmmode \tilde{}\else \~{}\fi{}}{n}(\mathrm{r})$, $\frac{\stackrel{\ifmmode \tilde{}\else \~{}\fi{}}{n}}{{n}_{0}}\ensuremath{\ll}1$, and (2) $n(\mathrm{r})=\ensuremath{\phi}(\frac{\mathrm{r}}{{r}_{0}})$ with $\ensuremath{\phi}$ arbitrary and ${r}_{0}\ensuremath{\rightarrow}\ensuremath{\infty}$. In both cases $F$ can be expressed entirely in terms of the correlation energy and linear and higher order electronic polarizabilities of a uniform electron gas. This approach also sheds some light on generalized Thomas-Fermi methods and their limitations. Some new extensions of these methods are presented.

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33,880 Citations

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Abstract: By considering a radiating gas as a single quantum-mechanical system, energy levels corresponding to certain correlations between individual molecules are described. Spontaneous emission of radiation in a transition between two such levels leads to the emission of coherent radiation. The discussion is limited first to a gas of dimension small compared with a wavelength. Spontaneous radiation rates and natural line breadths are calculated. For a gas of large extent the effect of photon recoil momentum on coherence is calculated. The effect of a radiation pulse in exciting "super-radiant" states is discussed. The angular correlation between successive photons spontaneously emitted by a gas initially in thermal equilibrium is calculated.

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Topics: Photon (56%), Spontaneous emission (54%), Thermal equilibrium (52%) ... show more

5,048 Citations

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01 Jan 1963-

Abstract: This paper has two purposes: 1) to clarify the relationship between the quantum theory of radiation, where the electromagnetic field-expansion coefficients satisfy commutation relations, and the semiclassical theory, where the electromagnetic field is considered as a definite function of time rather than as an operator; and 2) to apply some of the results in a study of amplitude and frequency stability in a molecular beam maser. In 1), it is shown that the semiclassical theory, when extended te take into account both the effect of the field on the molecules and the effect of the molecules on the field, reproduces almost quantitatively the same laws of energy exchange and coherence properties as the quantized field theory, even in the limit of one or a few quanta in the field mode. In particular, the semiclassical theory is shown to lead to a prediction of spontaneous emission, with the same decay rate as given by quantum electrodynamics, described by the Einstein A coefficients. In 2), the semiclassical theory is applied to the molecular beam maser. Equilibrium amplitude and frequency of oscillation are obtained for an arbitrary velocity distribution of focused molecules, generalizing the results obtained previously by Gordon, Zeiger, and Townes for a singel-velocity beam, and by Lamb and Helmer for a Maxwellian beam. A somewhat surprising result is obtained; which is that the measurable properties of the maser, such as starting current, effective molecular Q, etc., depend mostly on the slowest 5 to 10 per cent of the molecules. Next we calculate the effect of amplitude and frequency of oscillation, of small systematic perturbations. We obtain a prediction that stability can be improved by adjusting the system so that the molecules emit all their energy h Ω to the field, then reabsorb part of it, before leaving the cavity. In general, the most stable operation is obtained when the molecules are in the process of absorbing energy from the radiation as they leave the cavity, most unstable when they are still emitting energy at that time. Finally, we consider the response of an oscillating maser to randomly time-varying perturbations. Graphs are given showing predicted response to a small superimposed signal of a frequency near the oscillation frequency. The existence of "noise enhancing" and "noise quieting" modes of operation found here is a general property of any oscillating system in which amplitude is limited by nonlinearity.

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Topics: Semiclassical physics (59%), Quantum (55%), Electromagnetic field (55%) ... show more

3,567 Citations

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Abstract: The behaviour of strongly correlated materials, and in particular unconventional superconductors, has been studied extensively for decades, but is still not well understood. This lack of theoretical understanding has motivated the development of experimental techniques for studying such behaviour, such as using ultracold atom lattices to simulate quantum materials. Here we report the realization of intrinsic unconventional superconductivity-which cannot be explained by weak electron-phonon interactions-in a two-dimensional superlattice created by stacking two sheets of graphene that are twisted relative to each other by a small angle. For twist angles of about 1.1°-the first 'magic' angle-the electronic band structure of this 'twisted bilayer graphene' exhibits flat bands near zero Fermi energy, resulting in correlated insulating states at half-filling. Upon electrostatic doping of the material away from these correlated insulating states, we observe tunable zero-resistance states with a critical temperature of up to 1.7 kelvin. The temperature-carrier-density phase diagram of twisted bilayer graphene is similar to that of copper oxides (or cuprates), and includes dome-shaped regions that correspond to superconductivity. Moreover, quantum oscillations in the longitudinal resistance of the material indicate the presence of small Fermi surfaces near the correlated insulating states, in analogy with underdoped cuprates. The relatively high superconducting critical temperature of twisted bilayer graphene, given such a small Fermi surface (which corresponds to a carrier density of about 1011 per square centimetre), puts it among the superconductors with the strongest pairing strength between electrons. Twisted bilayer graphene is a precisely tunable, purely carbon-based, two-dimensional superconductor. It is therefore an ideal material for investigations of strongly correlated phenomena, which could lead to insights into the physics of high-critical-temperature superconductors and quantum spin liquids.

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Topics: Bilayer graphene (64%), Quantum oscillations (59%), Strongly correlated material (59%) ... show more

3,452 Citations