Nonlinear couplings between photons and electrons in new materials give rise to a wealth of interesting nonlinear phenomena [1]. This includes frequency mixing, optical rectification or nonlinear current generation, which are of particular interest for generating radiation in spectral regions that are difficult to access, such as the terahertz gap. Owing to its specific linear dispersion and high electron mobility at room temperature, graphene is particularly attractive for realizing strong nonlinear effects [2]. However, since graphene is a centrosymmetric material, second-order nonlinearities a priori cancel, which imposes to rely on less attractive third-order nonlinearities [3]. It was nevertheless recently demonstrated that dc-second-order nonlinear currents [4] as well as ultrafast ac-currents [5] can be generated in graphene under optical excitation. The asymmetry is introduced by the excitation at oblique incidence, resulting in the transfer of photon momentum to the electron system, known as the

We demonstrate the accuracy and efficiency of a recently introduced approach to account for nuclear quantum effects (NQEs) in molecular simulations: the adaptive quantum thermal bath (adQTB). In this method, zero-point energy is introduced through a generalized Langevin thermostat designed to precisely enforce the quantum fluctuation−dissipation theorem. We propose a refined adQTB algorithm with improved accuracy and report adQTB simulations of liquid water. Through extensive comparison with reference path integral calculations, we demonstrate that it provides excellent accuracy for a broad range of structural and thermodynamic observables as well as infrared vibrational spectra. The adQTB has a computational cost comparable to that of classical molecular dynamics, enabling simulations of up to millions of degrees of freedom.

Quantum thermal bath (QTB) simulations reproduce statistical nuclear quantum effects via a Langevin equation with a colored random force. Although this approach has proven efficient for a variety of chemical and condensed-matter problems, the QTB, as many other semiclassical methods, suffers from zero-point energy leakage (ZPEL). The absence of a reliable criterion to quantify the ZPEL without resorting to demanding comparisons with path integral based calculations has so far hindered the use of the QTB for the simulation of real systems. In this work, we establish a quantitative connection between ZPEL in the QTB framework and deviations from the quantum fluctuation-dissipation theorem (FDT) that can be monitored along the simulation. This provides a rigorous general criterion to detect and quantify the ZPEL without any a priori knowledge of the system under study. We then use this criterion to build an adaptive QTB method that strictly enforces the quantum FDT at all frequencies via an on-the-fly, spectrally resolved fine tuning of the system-bath coupling coefficients. The validity of the adaptive approach is first demonstrated on a simple two-oscillator model. It is then applied to two more realistic problems: the description of the vibrational properties of a model aluminium crystal at low temperature and the simulation of the liquid-solid phase transition in a 13-atom neon cluster. In both systems, the standard QTB results are strongly altered by the ZPEL, which can be essentially eliminated using the adaptive approach.

Strong and ultra-strong light-matter coupling are remarkable phenomena of quantum electrodynamics occurring when the interaction between a matter excitation and the electromagnetic field cannot be described by usual perturbation theory. This is generally achieved by coupling an excitation with large oscillator strength to the confined electromagnetic mode of an optical microcavity. In this work we demonstrate that strong/ultra-strong coupling can also take place in the absence of optical confinement. We have studied the non-perturbative spontaneous emission of collective excitations in a dense two-dimensional electron gas that supperradiantly decays into free space. By using a quantum model based on the input-output formalism, we have derived the linear optical properties of the coupled system and demonstrated that its eigenstates are mixed light-matter particles, like in any system displaying strong or ultra-strong light-matter interaction. Moreover, we have shown that in the ultra-strong coupling regime, i.e. when the radiative broadening is comparable to the matter excitation energy, the commonly used rotating-wave and Markov approximations yield unphysical results. Finally, the input-output formalism has allowed us to prove that Kirchhoff's law, describing thermal emission properties, applies to our system in all the light-matter coupling regimes considered in this work.

We introduce a new parametrization of the AMOEBA polarizable force field for water denoted Q-AMOEBA, for use in simulations that explicitly account for nuclear quantum effects (NQEs). This study is made possible thanks to the recently introduced adaptive Quantum Thermal Bath (adQTB) simulation technique which computational cost is comparable to classical molecular dynamics. The flexible Q-AMOEBA model conserves the initial AMOEBA functional form, with an intermolecular potential including an atomic multipole description of electrostatic interactions (up to quadrupole), a polarization contribution based on the Thole interaction model and a buffered 14–7 potential to model van der Waals interactions. It has been obtained by using a ForceBalance fitting strategy including high-level quantum chemistry reference energies and selected condensed-phase properties targets. The final Q-AMOEBA model is shown to accurately reproduce both gas-phase and condensed-phase properties, notably improving the original AMOEBA water model. This development allows the fine study of NQEs on water liquid phase properties such as the average H–O–H angle compared to its gas-phase equilibrium value, isotope effects, and so on. Q-AMOEBA also provides improved infrared spectroscopy prediction capabilities compared to AMOEBA03. Overall, we show that the impact of NQEs depends on the underlying model functional form and on the associated strength of hydrogen bonds. Since adQTB simulations can be performed at near classical computational cost using the Tinker-HP package, Q-AMOEBA can be extended to organic molecules, proteins, and nucleic acids opening the possibility for the large-scale study of the importance of NQEs in biophysics.

The Wigner thermal density is a function of considerable interest in the area of approximate (linearized or semiclassical) quantum dynamics where it is employed to generate initial conditions for the propagation of appropriate sets of classical trajectories. In this paper, we propose an original approach to compute the Wigner density, based on a generalized Langevin equation. The stochastic dynamics is non-trivial in that it contains a coordinate-dependent friction coefficient and a generalized force that couples momenta and coordinates. These quantities are, in general, not known analytically and have to be estimated via auxiliary calculations. The performance of the new sampling scheme is tested on standard model systems with highly non classical features such as relevant zero point energy effects, correlation between momenta and coordinates, and negative parts of the Wigner density. In its current brute force implementation, the algorithm, whose convergence can be systematically checked, is accurate and has only limited overhead compared to schemes with similar characteristics. We briefly discuss potential ways to further improve its numerical efficiency.

The performance of different approximate algorithms for computing anharmonic features in vibrational spectra is analysed and compared on model and more realistic systems that present relevant nuclear quantum effects. The methods considered combine approximate sampling of the quantum thermal distribution with classical time propagation and include Matsubara dynamics, path integral dynamics approaches, linearized initial value representation and the recently introduced adaptive quantum thermal bath. A perturbative analysis of these different methods enables to account for the observed numerical performance on prototypes for overtones and combination bands and to draw qualitatively correct trends for the numerical results obtained for Fermi resonances. Our results prove that the unequal performances of these approaches often derive from the method employed to sample initial conditions and not, as usually assumed, from the lack of coherence in the time propagation. Furthermore, as confirmed by the analysis reported in J. Chem. Phys. 130, 194510 (2021), we demonstrate, both via the perturbative approach and numerically, that path integral dynamics methods fail to reproduce the intensities of these anharmonic features and follow purely classical trends with respect to their temperature behaviour. Finally, the remarkably accurate performance of the adaptive quantum thermal bath approach is documented and motivated.

We study the incandescence of a semiconductor system characterized by a radiatively broadened material excitation. We show that the shape of the emission spectrum and the peak emissivity value are determined by the ratio between radiative and nonradiative relaxation rates of the material mode. Our system is a heavily doped quantum well, exhibiting a collective bright electronic excitation in the mid-infrared. The spontaneous emission rate of this collective mode strongly depends on the emission direction and, uncommonly for an intersubband system, can dominate nonradiative scattering processes. Consequently the incandescence spectrum undergoes strong modifications when the detection angle is varied. Incandescence is modeled solving quantum Langevin equations, including a microscopic description of the collective excitations, decaying into electronic and photonic baths. We demonstrate that the emissivity reaches unity value for a well-defined direction and presents an angular radiative pattern that is very different from that of an oscillating dipole.