arXiv:2407.03576 · The Journal of Chemical Physics
A simple fourth order propagator based on the Magnus expansion in the Liouville space: Application to a Λ-system and assessment of the rotating wave approximation
A simple fourth-order propagator [Ture and Jang, J. Phys. Chem. A 128, 2871 (2024)] based on the Magnus expansion is extended to the Liouville space for both closed-system and Lindbladian open-system quantum dynamics. For both dynamics, commutator free versions of fourth-order propagators are provided as well. These propagators are then applied to the dynamics of a driven Λ-system, where Lindblad terms represent the effect of a photonic bath. For both dynamics, the accuracy of the rotating wave approximation (RWA) for the matter-radiation interaction is assessed. We confirmed reasonable performance of RWA for weak and resonant fields. However, small errors appear for moderate fields and substantial errors can be found for strong fields where coherent population trapping can still be expected. We also found that the presence of bath for open-system quantum dynamics consistently reduces the errors of the RWA. These results provide quantitative information on how the RWA breaks down beyond weak field or for non-resonant cases. Major results are benchmarked against results of our sixth-order ME-based propagator. We also provide numerical comparison of our algorithms with other fourth-order algorithms for the Λ-system. These confirm reasonable performance of our simple propagators and the improvement gained through commutator-free expressions.
A simple fourth-order propagator [Ture and Jang, J. Phys. Chem. A 128, 2871 (2024)] based on the Magnus expansion is extended to the Liouville space for both closed-system and Lindbladian open-system quantum dynamics. For both dynamics, commutator free versions of fourth-order propagators are provided as well. These propagators are then applied to the dynamics of a driven Λ-system, where Lindblad terms represent the effect of a photonic bath. For both dynamics, the accuracy of the rotating wave approximation (RWA) for the matter-radiation interaction is assessed. We confirmed reasonable performance of RWA for weak and resonant fields. However, small errors appear for moderate fields and substantial errors can be found for strong fields where coherent population trapping can still be expected. We also found that the presence of bath for open-system quantum dynamics consistently reduces the errors of the RWA. These results provide quantitative information on how the RWA breaks down beyond weak field or for non-resonant cases. Major results are benchmarked against results of our sixth-order ME-based propagator. We also provide numerical comparison of our algorithms with other fourth-order algorithms for the Λ-system. These confirm reasonable performance of our simple propagators and the improvement gained through commutator-free expressions.
Magnus expansion (ME) provides a general way to expand the real-time propagator of a time-dependent Hamiltonian within the exponential such that the unitarity is satisfied at any order. We use this property and explicit integration of Lagrange interpolation formulas for the time-dependent Hamiltonian within each time interval and derive approximations that preserve unitarity for the differential time evolution operators of general time-dependent Hamiltonians. The resulting second-order approximation is the same as using the average of Hamiltonians for two end points of time. We identify three fourth-order approximations involving commutators of Hamiltonians at different times and also derive a sixth-order expression. A test of these approximations along with other available expressions for a two-state time-dependent Hamiltonian with sinusoidal time dependences provides information on the relative performance of these approximations and suggests that the derived expressions can serve as useful numerical tools for time evolution in time-resolved spectroscopy, quantum control, quantum sensing, real-time ab initio quantum dynamics, and open system quantum dynamics.
We study the stochastic dynamics of a two-level quantum system interacting with a stochastic magnetic field, and a single frequency electromagnetic field, with and without making the rotating wave approximation (RWA). The transformation to the rotating frame does not commute with the stochastic Hamiltonian if the stochastic field has nonvanishing components in the transverse direction. Hence, making the RWA modifies the stochastic terms in the Hamiltonian. Modification of the decay terms is also required in a master equation approach (i.e., the Liouville--von Neumann density matrix equation) for describing the dynamics. For isotropic Gaussian white noise, the RWA dynamics remains Markovian, although the Lindblad terms in the master equation for the density matrix become time-dependent when the non-commutation of the RWA transformation and the noise Hamiltonian is properly accounted for. We also treat Ornstein--Uhlenbeck noise, and find, in contra-distinction to the white noise case, a significant difference in the dynamics calculated with the RWA when the non-commutation of the RWA transformation and the noise Hamiltonian is taken into account. These findings are applicable to the modeling of any open quantum system coupled to an electromagentic field.
Hybrid quantum-classical systems combine both classical and quantum degrees of freedom. Typically, in Chemistry, Molecular Physics, or Materials Science, the classical degrees of freedom describe atomic nuclei (or cations with frozen core electrons), whereas the quantum particles are the electrons. Although many possible hybrid dynamical models exist, the basic one is the so-called Ehrenfest dynamics that results from the straightforward partial classical limit applied to the full quantum Schrödinger equation. Few numerical methods have been developed specifically for the integration of this type of systems. Here we present a preliminary study of the performance of a family of recently developed propagators: the (quasi) commutator-free Magnus expansions. These methods, however, were initially designed for nonautonomous linear equations. We employ them for the nonlinear Ehrenfest system, by approximating the state value at each time step in the propagation, using an extrapolation from previous time steps.
Open quantum systems are often described by a Lindblad master equation, which relies on a set of approximations, most importantly the rotating-wave approximation which is only valid for weak damping. In the Lindblad setting, dissipative processes are described through jump operators, distinguishing between absorption and emission of photons. This enables the simple identification of emitted photons which provides a straightforward way to obtain the radiation statistics. Outside the rotating-wave limit, the Lindblad approach does not work. Open quantum systems can then be described by, e.g., the quantum Langevin equation. However, in this framework the number of emitted photons is not easily accessible. In this work, we point out how to obtain the photon counting statistics from a quantum Langevin equation and provide an expression for the photon current operator, for arbitrary systems coupled to linear environments. As an example, we employ the method to study the radiation statistics of a damped harmonic oscillator at finite temperature beyond the rotating-wave approximation. We show that even outside the rotating-wave limit, the most important contribution to the radiation statistics can be captured by an effective Lindblad equation, thus extending the range of possible applications of the Lindblad framework.
We consider the numerical propagation of models that combine both quantum and classical degrees of freedom, usually, electrons and nuclei, respectively. We focus, in our computational examples, on the case in which the quantum electrons are modeled with time-dependent density-functional theory, although the methods discussed below can be used with any other level of theory. Often, for these so-called quantum-classical molecular dynamics models, one uses some propagation technique to deal with the quantum part and a different one for the classical equations. While the resulting procedure may, in principle, be consistent, it can however spoil some of the properties of the methods, such as the accuracy order with respect to the time step or the preservation of the geometrical structure of the equations. Few methods have been developed specifically for hybrid quantum-classical models. We propose using the same method for both the quantum and classical particles, in particular, one family of techniques that proves to be very efficient for the propagation of Schrödinger-like equations: the (quasi)-commutator free Magnus expansions. These have been developed, however, for linear systems, yet our problem is nonlinear: formally, the full quantum-classical system can be rewritten as a nonlinear Schrödinger equation, i.e., one in which the Hamiltonian depends on the system itself. The Magnus expansion algorithms for linear systems require the application of the Hamiltonian at intermediate points in a given propagating interval. For nonlinear systems, this poses a problem as this Hamiltonian is unknown due to its dependence on the state. We approximate it by employing a higher order extrapolation using previous steps as input. The resulting technique can then be regarded as a multistep technique or, alternatively, as a predictor corrector formula.
Away from equilibrium, the properties of open quantum systems depend on the details of their environment. A microscopic derivation of a master equation (ME) is therefore crucial. Of particular interest are Lindblad-type equations, not only because they provide the most general class of Markovian MEs, but also since they are the starting point for efficient quantum trajectory simulations. Lindblad-type MEs are commonly derived from the Born-Markov-Redfield equation via a rotating-wave approximation (RWA). However the RWA is valid only for ultraweak system-bath coupling and often fails to accurately describe nonequilibrium processes. Here we derive an alternative Lindbladian approximation to the Redfield equation, which does not rely on ultraweak system-bath coupling. Applying it to an extended Hubbard model coupled to Ohmic baths, we show that, especially away from equilibrium, it provides a good approximation in large parameter regimes where the RWA fails.