A quantum problem of the evolution of a system coupled to a reservoir for which the interlevel spacing monotonically increases or decreases with increasing energy was solved. It was demonstrated that, despite the absence of an unambiguous definition of the recurrence cycle period, there is a wide range of parameters within which the basic feature of the evolution of system with an equidistant spectrum persist: the existence of the Loschmidt echo and mixing of the cycles that initiates the transition from a regular to a stochastic dynamic behavior. The results predict the existence of nonergodic nanosystems in which, as they evolve, energy periodically concentrates on certain vibrational degrees of freedom.
A quantum problem of the evolution of a system coupled to a reservoir for which the interlevel spacing monotonically increases or decreases with increasing energy was solved. It was demonstrated that, despite the absence of an unambiguous definition of the recurrence cycle period, there is a wide range of parameters within which the basic feature of the evolution of system with an equidistant spectrum persist: the existence of the Loschmidt echo and mixing of the cycles that initiates the transition from a regular to a stochastic dynamic behavior. The results predict the existence of nonergodic nanosystems in which, as they evolve, energy periodically concentrates on certain vibrational degrees of freedom.
Abstract Small (but still containing many, about 102–104, atoms) quantum systems (traditionally termed nano-systems) are dramatically different from their macroscopic or genuine microscopic (atomic) cousins. Microscopic molecular systems (with a few atoms) obey a regular quantum dynamics (described by time dependent Schrödinger equation), whereas in macroscopic systems with continuous energy spectra, one can expect, also regular, although typically relaxation, dynamic behavior. The topic of our paper is in between these limits. Nano-scale systems are characterized by small (but finite) mean interlevel spacing. In such a case with recurrence periods in picosecond range, Loschmidt echo and double resonance phenomena come into the game. System behavior becomes nontrivial and manifests a sort of transitions between regular and chaotic dynamics. We show that such dynamic transitions occur when the Loschmidt echo time of life exceeds the typical recurrence cycle period. We illustrate this behavior in the frame work of a few versions of the exactly solvable quantum problem, proposed long ago by Zwanzig. It is based on the study of time evolution of the initially prepared vibrational state coupled to a reservoir with dense spectrum of its vibrational states. In the simplest version of the Zwanzig model, the reservoir has an equidistant spectrum, and the system—reservoir coupling matrix elements are independent of the reservoir states. We generalize the model to include into consideration the coupling of the initially prepared single state to system phonon excitations. The coupling results to temperature dependent broadening and decay of the echo components. Another generalization is to replace a single level by two states coupled to the Zwanzig reservoir. We anticipate that the basic ideas inspiring our work can be applied to a large variety of interesting for the applications nanosystems (e.g., dissipative free propagation of excitations along molecular chains, or as a model for exchange reactions).
The time evolution of a prepared vibrational state (system) coupled to a reservoir with a dense spectrum of its vibrational states has been investigated under the assumption that the reservoir has an equidistant spectrum, and the system-reservoir coupling matrix elements are independent of the reservoir states. The analytical solution manifests three regimes of the evolution for the system: (i) weakly damped oscillations; (ii) a multicomponent Loschmidt echo in recurrence cycles; and (iii) overlapping recurrence cycles. We find the characteristic critical values of the system-reservoir coupling constant for the transitions between these regimes. Stochastic dynamics occurs in regime (iii) due to an unavoidably, in any real system, coarse graining of the time or energy measurements or the initial condition uncertainty. At any finite accuracy, one can always find the cycle number k c when the dynamics of the system for k>k c cannot be determined uniquely from the spectrum, and, in this sense, the long-time system evolution becomes chaotic. Even though a specific toy model is investigated here, when properly interpreted, it yields quite a reasonable description for a variety of physically relevant phenomena, such as the complex vibrational dynamics of nanoparticles with characteristic interlevel spacing on the order of 10 cm−1 observed using subpicosecond spectroscopy methods.
Small (but still containing many, about 10 2 -10 4 , atoms) quantum systems (traditionally termed nano-systems) are dramatically different from their macroscopic or genuine microscopic (atomic) cousins.Microscopic molecular systems (with a few atoms) obey a regular quantum dynamics (described by time dependent Schrodinger equation), whereas in macroscopic systems with continuous energy spectra, one can expect, also regular, although typically relaxation, dynamic behavior.The topic of our paper is in-between these limits.Nano-scale systems are characterized by small (but finite) mean inter-level spacing.In such a case with recurrence periods in pico-second range, Loschmidt echo and double resonance phenomena come into the game.System behavior becomes non-trivial and manifests a sort of transitions between regular and chaotic dynamics.We show that such dynamic transitions occur when the Loschmidt echo time of life exceeds the typical recurrence cycle period.We illustrate this behavior in the frame work of a few versions of the exactly solvable quantum problem, proposed long ago by Zwanzig.It is based on the study of time evolution of the initially prepared vibrational state coupled to a reservoir with dense spectrum of its vibrational states.In the simplest version of the Zwanzig model, the reservoir has an equidistant spectrum, and the system -reservoir coupling matrix elements are independent of the reservoir states.We generalize the model to include into consideration the coupling of the initially prepared single state to system phonon excitations.The coupling results to temperature dependent broadening and decay of the echo components.Another generalization is to replace a single level by two states coupled to the Zwanzig reservoir.We anticipate that the basic ideas inspiring our work can be applied to a large variety of interesting for the applications nano-systems (e.g., dissipative free propagation of excitations along molecular chains, or as a model for exchange reactions).
In the framework of a simple spin-boson Hamiltonian we study an interplay between dynamic and spectral roots to stochastic-like behavior. The Hamiltonian describes an initial vibrational state coupled to discrete dense spectrum reservoir. The reservoir states are formed by three sequences with rationally independent periodicities 1; 1 ± δ typical for vibrational states in many nanosize systems (e.g., large molecules containing CH2 fragment chains, or carbon nanotubes). We show that quantum evolution of the system is determined by a dimensionless parameter δΓ, where Γ is characteristic number of the reservoir states relevant for the initial vibrational level dynamics. When δΓ > 1 spectral chaos destroys recurrence cycles and the system state evolution is stochastic-like. In the opposite limit δΓ < 1 dynamics is regular up to the critical recurrence cycle k c and for larger k > k c dynamic mixing leads to quasi-stochastic time evolution. Our semi-quantitative analytic results are confirmed by numerical solution of the equation of motion. We anticipate that both kinds of stochastic-like behavior (namely, due to spectral mixing and recurrence cycle dynamic mixing) can be observed by femtosecond spectroscopy methods in nanosystems in the spectral window 1011–1013 s−1
The quantum dynamical problem is solved for a system coupled to an equidistant-spectrum bath with the energy difference Ω between the neighboring levels n and n + 1 and the coupling matrix elements C 2 = C 2(1 + Δ−2 n 2)−1 constraining the energy interval comprising the bath states interacting with the system. The evolution in the strong-coupling limit is determined by two parameters, Γ = πC 2/Ω ≫ 1 and α = Γ/Δ. If α ≠ 0, then the decrease in the population in the initial cycle with a period of 2π/Ω is not exponential and the effective rate constant increases with time. The results qualitatively explain the appearance of nonexponential relaxation regimes for a dense-spectrum nanosystem and predict the possibility of the multiple recovery of the initial-state population.
The quantum dynamics of a simple model of a nanoparticle has been investigated. This model suggests that the initially prepared state (system) interacts with the other states (reservoir) forming a dense discrete spectrum. In contrast to our previous papers concerned with this problem [1, 2], in which only the dynamics of the system has been studied, the present paper is devoted to the description of the evolution of reservoir states. In the initial recurrence cycles, the reverse transitions from the reservoir to the system generate a double resonance (an echo at frequencies of the reservoir states transitions). Since different states of the reservoir are depleted at different instants of time, the Loschmidt echo in the system is inhomogeneously broadened, whereas the double resonances remain narrower and more intense. Apart from the main resonances, there arise satellites due to the redistribution of the populations between the reservoir states during the cycle. In mixing cycles regime, the regular evolution of the reservoir states (like the system state) transforms into a stochastic-like evolution. It is noted that the predicted double resonances can be experimentally detected and used in analyzing vibrational relaxation of large molecules and nanoparticles.