We present a general approach to derive Lindblad master equations for a subsystem whose dynamics is coupled
to dissipative bosonic modes. The derivation relies on a Schrieffer-Wolff transformation which allows to
eliminate the bosonic degrees of freedom after self-consistently determining their state as a function of the coupled quantum system. We apply this formalism to the dissipative Dicke model and derive a Lindblad master equation for the atomic spins, which includes the coherent and dissipative interactions mediated by the bosonic mode. This master equation accurately predicts the Dicke phase transition and gives the correct steady state. In addition, we compare the dynamics using exact diagonalization and numerical integration of the master equation with the predictions of semiclassical trajectories. We finally test the performance of our formalism by studying the relaxation of a NOON state and show that the dynamics captures quantum metastability beyond the mean-field approximation.
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Incorporating Lindblad Decay Dynamics into Mixed Quantum-Classical Simulations
We derive the $\mathcal{L}$-MFE method to incorporate Lindblad jump operator dynamics into the mean-field Ehrenfest (MFE) approach. We map the density matrix evolution of Lindblad dynamics onto pure state coefficients using trajectory averages. We use simple assumptions to construct the $\mathcal{L}$-MFE method that satisfies this exact mapping. This establishes a method that uses independent trajectories which exactly reproduces Lindblad decay dynamics using a wavefunction description, with deterministic changes of the magnitudes of the quantum expansion coefficients, while only adding on a stochastic phase. We further demonstrate that when including nuclei in the Ehrenfest dynamics, the $\mathcal{L}$-MFE method gives semi-quantitatively accurate results, with the accuracy limited by the accuracy of the approximations present in the semiclassical MFE approach. This work provides a general framework to incorporate Lindblad dynamics into semiclassical or mixed quantum-classical simulations.
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- Award ID(s):
- 2124398
- NSF-PAR ID:
- 10346907
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Within the nuclear-electronic orbital (NEO) framework, the real-time NEO time-dependent density functional theory (RT-NEO-TDDFT) approach enables the simulation of coupled electronic-nuclear dynamics. In this approach, the electrons and quantum nuclei are propagated in time on the same footing. A relatively small time step is required to propagate the much faster electronic dynamics, thereby prohibiting the simulation of long-time nuclear quantum dynamics. Herein, the electronic Born–Oppenheimer (BO) approximation within the NEO framework is presented. In this approach, the electronic density is quenched to the ground state at each time step, and the real-time nuclear quantum dynamics is propagated on an instantaneous electronic ground state defined by both the classical nuclear geometry and the nonequilibrium quantum nuclear density. Because the electronic dynamics is no longer propagated, this approximation enables the use of an order-of-magnitude larger time step, thus greatly reducing the computational cost. Moreover, invoking the electronic BO approximation also fixes the unphysical asymmetric Rabi splitting observed in previous semiclassical RT-NEO-TDDFT simulations of vibrational polaritons even for small Rabi splitting, instead yielding a stable, symmetric Rabi splitting. For the intramolecular proton transfer in malonaldehyde, both RT-NEO-Ehrenfest dynamics and its BO counterpart can describe proton delocalization during the real-time nuclear quantum dynamics. Thus, the BO RT-NEO approach provides the foundation for a wide range of chemical and biological applications.
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Solving the time-dependent Schrödinger equation is an important application area for quantum algorithms. We consider Schrödinger's equation in the semi-classical regime. Here the solutions exhibit strong multiple-scale behavior due to a small parameter ℏ , in the sense that the dynamics of the quantum states and the induced observables can occur on different spatial and temporal scales. Such a Schrödinger equation finds many applications, including in Born-Oppenheimer molecular dynamics and Ehrenfest dynamics. This paper considers quantum analogues of pseudo-spectral (PS) methods on classical computers. Estimates on the gate counts in terms of ℏ and the precision ε are obtained. It is found that the number of required qubits, m , scales only logarithmically with respect to ℏ . When the solution has bounded derivatives up to order ℓ , the symmetric Trotting method has gate complexity O ( ( ε ℏ ) − 1 2 p o l y l o g ( ε − 3 2 ℓ ℏ − 1 − 1 2 ℓ ) ) , provided that the diagonal unitary operators in the pseudo-spectral methods can be implemented with p o l y ( m ) operations. When physical observables are the desired outcomes, however, the step size in the time integration can be chosen independently of ℏ . The gate complexity in this case is reduced to O ( ε − 1 2 p o l y l o g ( ε − 3 2 ℓ ℏ − 1 ) ) , with ℓ again indicating the smoothness of the solution.more » « less
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Sodium hydride (NaH) in the gas phase presents a seemingly simple electronic structure making it a potentially tractable system for the detailed investigation of nonadiabatic molecular dynamics from both computational and experimental standpoints. The single vibrational degree of freedom, as well as the strong nonadiabatic coupling that arises from the excited electronic states taking on considerable ionic character, provides a realistic chemical system to test the accuracy of quasi-classical methods to model population dynamics where the results are directly comparable against quantum mechanical benchmarks. Using a simulated pump–probe type experiment, this work presents computational predictions of population transfer through the avoided crossings of NaH via symmetric quasi-classical Meyer–Miller (SQC/MM), Ehrenfest, and exact quantum dynamics on realistic, ab initio potential energy surfaces. The main driving force for population transfer arises from the ground vibrational level of the D 1 Σ + adiabatic state that is embedded in the manifold of near-dissociation C 1 Σ + vibrational states. When coupled through a sharply localized first-order derivative coupling most of the population transfers between t = 15 and t = 30 fs depending on the initially excited vibronic wavepacket. While quantum mechanical effects are expected due to the reduced mass of NaH, predictions of the population dynamics from both the SQC/MM and Ehrenfest models perform remarkably well against the quantum dynamics benchmark. Additionally, an analysis of the vibronic structure in the nonadiabatically coupled regime is presented using a variational eigensolver methodology.more » « less
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Abstract We study the trajectories of a semiclassical quantum particle under repeated indirect measurement by Kraus operators, in the setting of the quantized torus. In between measurements, the system evolves via either Hamiltonian propagators or metaplectic operators. We show in both cases the convergence in total variation of the quantum trajectory to its corresponding classical trajectory, as defined by the propagation of a semiclassical defect measure. This convergence holds up to the Ehrenfest time of the classical system, which is larger when the system is “less chaotic.” In addition, we present numerical simulations of these effects. In proving this result, we provide a characterization of a type of semi-classical defect measure we call uniform defect measures. We also prove derivative estimates of a function composed with a flow on the torus.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0099922
