Calculation of two-time-correlation functions in Liouville space

Vladimir Chernyak, Shaul Mukamel

A time-dependent functional approach is developed for calculating the dynamical optical response and ground-state properties of nonrelativistic fermion systems. The functional (effective action) uses the particle-hole components of the reduced single-electron density matrix as variables and is constructed using the natural orbitals as a reference. It is defined on pairs of trajectories that constitute a Liouville space path in the phase space of the classical analog of the quantum system. A perturbative ``semiclassical'' calculation of the effective Liouville-space action is used to incorporate correlation effects in the linear optical response.

Dave Thirumalai, B. J. Berne

Roger Balian, M. Vénéroni

Jian Liu, William Hughes Miller

We show the exact expression of the quantum mechanical time correlation function in the phase space formulation of quantum mechanics. The trajectory-based dynamics that conserves the quantum canonical distribution-equilibrium Liouville dynamics (ELD) proposed in Paper I is then used to approximately evaluate the exact expression. It gives exact thermal correlation functions (of even nonlinear operators, i.e., nonlinear functions of position or momentum operators) in the classical, high temperature, and harmonic limits. Various methods have been presented for the implementation of ELD. Numerical tests of the ELD approach in the Wigner or Husimi phase space have been made for a harmonic oscillator and two strongly anharmonic model problems, for each potential autocorrelation functions of both linear and nonlinear operators have been calculated. It suggests ELD can be a potentially useful approach for describing quantum effects for complex systems in condense phase.

Meghan E. Halse, Jean‐Nicolas Dumez, Lyndon Emsley

The quasi-equilibrium behaviour of isolated nuclear spin systems in full and reduced Liouville spaces is discussed. We focus in particular on the reduced Liouville spaces used in the low-order correlations in Liouville space (LCL) simulation method, a restricted-spin-space approach to efficiently modelling the dynamics of large networks of strongly coupled spins. General numerical methods for the calculation of quasi-equilibrium expectation values of observables in Liouville space are presented. In particular, we treat the cases of a time-independent Hamiltonian, a time-periodic Hamiltonian (with and without stroboscopic sampling) and powder averaging. These quasi-equilibrium calculation methods are applied to the example case of spin diffusion in solid-state nuclear magnetic resonance. We show that there are marked differences between the quasi-equilibrium behaviour of spin systems in the full and reduced spaces. These differences are particularly interesting in the time-periodic-Hamiltonian case, where simulations carried out in the reduced space demonstrate ergodic behaviour even for small spins systems (as few as five homonuclei). The implications of this ergodic property on the success of the LCL method in modelling the dynamics of spin diffusion in magic-angle spinning experiments of powders is discussed.

Andriani Keliri, Marco Schirò

We study driven and open quantum systems described by a time-periodic Lindblad master equation. In closed systems, the stroboscopic dynamics can always be described by an effective time-independent Floquet Hamiltonian; this idea is the basis of Floquet engineering. However, in the presence of dissipation, the existence of an effective time-independent Floquet Lindbladian is not guaranteed due to the non-unitary nature of the evolution. Using Floquet theory, we construct a well-defined time-independent Floquet Lindbladian in an extended Sambe-Liouville space, transforming the initial time-dependent problem to a static and non-Hermitian eigenvalue problem. For harmonic driving, we introduce a matrix continued fraction method to nonperturbatively resum multiphoton processes and construct an effective Floquet Lindbladian acting only on the physical Liouville space. Compared to other high-frequency expansions, this method has the advantage of providing the whole infinite series expansion at once. Using a resolvent formalism, we show how to obtain a spectral Floquet representation of correlation functions of an open quantum system. As an application, we consider a dissipating two-level system in a linearly polarized field and calculate its resonance fluorescence spectrum. Furthermore, we consider a parametrically driven quantum dot with pump and loss for which we calculate its spectral function and current-voltage characteristics.