Generalized Langevin Equation and non-Markovian fluctuation-dissipation theorem for particle-bath systems in external oscillating fields

The Generalized Langevin Equation (GLE) can be derived from a particle-bath Hamiltonian, in both classical and quantum dynamics, and provides a route to the (both Markovian and non-Markovian) fluctuation-dissipation theorem (FDT). All previous studies have focused either on particle-bath systems with time-independent external forces only, or on the simplified case where only the tagged particle is subject to the external time-dependent oscillatory field. Here we extend the GLE and the corresponding FDT for the more general case where both the tagged particle and the bath oscillators respond to an external oscillatory field. This is the example of a charged or polarisable particle immersed in a bath of other particles that are also charged or polarizable, under an external AC electric field. For this Hamiltonian, we find that the ensemble average of the stochastic force is not zero, but proportional to the AC field. The associated FDT reads as $\langle F_P(t)F_P(t')\rangle=mk_BT\nu(t-t')+(\gamma e)^2E(t)E(t')$, where $F_{p}$ is the random force, $\nu(t-t')$ is the friction memory function, and $\gamma$ is a numerical prefactor

Collective response in light-matter interactions: The interplay between strong coupling and local dynamics

A model designed to mimic the implications of the collective optical response of molecular ensembles in optical cavities on molecular vibronic dynamics is investigated. Strong molecule-radiation field coupling is often reached when a large number N of molecules respond collectively to the radiation field. In electronic strong coupling, molecular nuclear dynamics following polariton excitation reflects (a) the timescale separation between the fast electronic and photonic dynamics and the slow nuclear motion on one hand, and (b) the interplay between the collective nature of the molecule-field coupling and the local nature of the molecules nuclear response on the other. The first implies that the electronic excitation takes place, in the spirit of the Born approximation, at an approximately fixed nuclear configuration. The second can be rephrased as the intriguing question, can the collective nature of the optical excitation lead to collective nuclear motion following polariton formation, resulting in so-called polaron decoupled dynamics. We address this issue by studying the dynamical properties of a simplified Holstein-Tavis-Cummings type model, in which boson modes representing molecular vibrations are replaced by two-level systems while the boson frequency and the vibronic coupling are represented by the coupling between these levels (that induces Rabi oscillations between them) and electronic state dependence of this coupling. We investigate the short-time behavior of this model following polariton excitation as well as its response to CW driving and its density of states spectrum. We find that, while some aspects of the dynamical behavior appear to adhere to the polaron decoupling picture, the observed dynamics mostly reflect the local nature of the nuclear configuration of the electronic polariton rather than this picture

Microscopic Theory of Linear Response in Amorphous Materials

This thesis provides an analytical and systematic framework from first-principles to study dielectric and mechanical properties of disordered materials, as well as non-centrosymmetric crystals. The Caldeira-Leggett Hamiltonian opens a route to the (both Markovian and nonMarkovian) fluctuation-dissipation theorem (FDT) and gives rise to the generalised Langevin equation (GLE) in classical dynamics. In the first place, I extend the GLE and the corresponding FDT for more general cases where both the tagged particle and bath oscillators respond to an external oscillatory field. This is the example of a charged or polarisable particle immersed in a bath of other particles that are also charged or polarisable, under an external AC electric field. Being linked to the vibrational density of states (VDOS), the dielectric function calculated based on the GLE is compared with experimental data for the paradigmatic case of molecular glasses: glycerol and Freons 112 & 113, around and above the glass transition temperature, Tg. Moving to the mechanical aspect, the theory of nonaffine lattice dynamics is able to describe the various relaxation processes in the linear viscoelastic response of metallic glasses. In particular, to understand universal properties of relaxation, the VDOS obtained in simulations, or in experiments, is substituted into the model. The nonaffine contribution to elasticity is also important for the pre-stressed/stretched harmonic networks. In order to give an insight on nonaffinity, I compute static elastic constants of α-quartz, taking into account the long-range Coulomb interaction. The nonaffine (softening) correction is found very large, such that the overall elastic constants are at least 3-4 times smaller than the affine Born-Huang estimate. Finally, I formulate the analytical expression of the dynamical structure factor by averaging over all quenched disorder along the acoustic branch, which stores the information of phonon transport in disordered materials. The Rayleigh scattering may be enhanced by a logarithmic factor in an intermediate range of wavenumber. I present a tensorial replica field-theoretic derivation based on heterogeneous or fluctuating elasticity, which suggests that long-range spatial correlations (in power-law decay) of elastic constants (or stress tensors) might be responsible for the logarithmic enhancement to Rayleigh scattering of phonons in amorphous solids.CSC-Cambridge scholarshi

Hyperballistic transport in dense ionized matter under external AC electric fields

The Langevin equation is ubiquitously employed to numerically simulate plasmas and dusty plasmas. However, the usual assumption of white noise becomes untenable when the system is subject to an external AC electric field. This is because the charged particles in the plasma, which provide the thermal bath for the particle transport, become themselves responsive to the AC field and the thermal noise is field-dependent and non-Markovian. We theoretically study the particle diffusivity in a Langevin transport model for a tagged charged particle immersed in a dense plasma of charged particles that act as the thermal bath, under an external AC electric field, by properly accounting for the effects of the AC field on the thermal bath statistics. We analytically derive the time-dependent generalized diffusivity $D(t)$ for different initial conditions. The generalized diffusivity exhibits damped oscillatory-like behaviour with initial very large peaks, where the generalized diffusion coefficient is enhanced by orders of magnitude with respect to the infinite-time steady-state value. The latter coincides with the Stokes-Einstein diffusivity in the absence of external field. For initial conditions where the external field is already on at $t=0$ and the system is thermalized under DC conditions for $t \leq 0$, the short-time behaviour is hyperballistic, $MSD \sim t^4$ (where MSD is the mean-squared displacement), leading to giant enhancement of the particle transport. Finally, the theory elucidates the role of medium polarization on the local Lorentz field, and allows for estimates of the effective electric charge due to polarization by the surrounding charges

Possible origin of β\beta-relaxation in amorphous metal alloys from atomic-mass differences of the constituents

We employ an atomic-scale theory within the framework of nonaffine lattice dynamics to uncover the origin of the Johari-Goldstein (JG) $\beta$-relaxation in metallic glasses (MGs). Combining simulation and experimental data with our theoretical approach, we reveal that the large mass asymmetry between the elements in a La$_{60}$Ni$_{15}$Al$_{25}$ MG leads to a clear separation in the respective relaxation time scales, giving strong evidence that JG relaxation is controlled by the lightest atomic species present. Moreover, we show that only qualitative features of the vibrational density of states determine the overall observed mechanical response of the glass, paving the way for a possible unified theory of secondary relaxations in glasses

Vibrational density of states of amorphous solids with long-ranged power-law-correlated disorder in elasticity.

A theory of vibrational excitations based on power-law spatial correlations in the elastic constants (or equivalently in the internal stress) is derived, in order to determine the vibrational density of states D([Formula: see text]) of disordered solids. The results provide the first prediction of a boson peak in amorphous materials where spatial correlations in the internal stresses (or elastic constants) are of power-law form, as is often the case in experimental systems, leading to a logarithmic enhancement of (Rayleigh) phonon attenuation. A logarithmic correction of the form [Formula: see text] is predicted to occur in the plot of the reduced excess DOS for frequencies around the boson peak in 3D. Moreover, the theory provides scaling laws of the density of states in the low-frequency region, including a [Formula: see text] regime in 3D, and provides information about how the boson peak intensity depends on the strength of power-law decay of fluctuations in elastic constants or internal stress. Analytical expressions are also derived for the dynamic structure factor for longitudinal excitations, which include a logarithmic correction factor, and numerical calculations are presented supporting the assumptions used in the theory

Disentangling α and β relaxation in orientationally disordered crystals with theory and experiments.

We use a microscopically motivated generalized Langevin equation (GLE) approach to link the vibrational density of states (VDOS) to the dielectric response of orientational glasses (OGs). The dielectric function calculated based on the GLE is compared with experimental data for the paradigmatic case of two OGs: freon-112 and freon-113, around and just above T_{g}. The memory function is related to the integral of the VDOS times a spectral coupling function γ(ω_{p}), which tells the degree of dynamical coupling between molecular degrees of freedom at different eigenfrequencies. The comparative analysis of the two freons reveals that the appearance of a secondary β relaxation in freon-112 is due to cooperative dynamical coupling in the regime of mesoscopic motions caused by stronger anharmonicity (absent in freon-113) and is associated with the comparatively lower boson peak in the VDOS. The proposed framework brings together all the key aspects of glassy physics (VDOS with the boson peak, dynamical heterogeneity, dissipation, and anharmonicity) into a single model