The quantum dynamics problem for a 1D chain consisting of 2 N + 1 sites ( N ≫ 1) with the interaction of nearest neighbors and an impurity site at the middle differing in energy and in coupling constant from the sites of the remaining chain is solved analytically. The initial excitation of the impurity is accompanied by the propagation of excitation over the chain sites and with the emergence of Loschmidt echo (partial restoration of the impurity site population) in the recurrence cycles with a period proportional to N . The echo consists of the main (most intense) component modulated by damped oscillations. The intensity of oscillations increases with increasing cycle number and matrix element C of the interaction of the impurity site n = 0 with sites n = ±1 (0 < C ≤ 1; for the remaining neighboring sites, the matrix element is equal to unity). Mixing of the components of echo from neighboring cycles induces a transition from the regular to stochastic evolution. In the regular evolution region, the wave packet propagates over the chain at a nearly constant group velocity, embracing a number of sites varying periodically with time. In the stochastic regime, the excitation is distributed over a number of sites close to 2 N , with the populations varying irregularly with time. The model explains qualitatively the experimental data on ballistic propagation of the vibrational energy in linear chains of CH 2 fragments and predicts the possibility of a nondissipative energy transfer between reaction centers associated with such chains.
The quantum dynamics problem for a 1D chain consisting of 2 N + 1 sites ( N ≫ 1) with the interaction of nearest neighbors and an impurity site at the middle differing in energy and in coupling constant from the sites of the remaining chain is solved analytically. The initial excitation of the impurity is accompanied by the propagation of excitation over the chain sites and with the emergence of Loschmidt echo (partial restoration of the impurity site population) in the recurrence cycles with a period proportional to N . The echo consists of the main (most intense) component modulated by damped oscillations. The intensity of oscillations increases with increasing cycle number and matrix element C of the interaction of the impurity site n = 0 with sites n = ±1 (0 < C ≤ 1; for the remaining neighboring sites, the matrix element is equal to unity). Mixing of the components of echo from neighboring cycles induces a transition from the regular to stochastic evolution. In the regular evolution region, the wave packet propagates over the chain at a nearly constant group velocity, embracing a number of sites varying periodically with time. In the stochastic regime, the excitation is distributed over a number of sites close to 2 N , with the populations varying irregularly with time. The model explains qualitatively the experimental data on ballistic propagation of the vibrational energy in linear chains of CH 2 fragments and predicts the possibility of a nondissipative energy transfer between reaction centers associated with such chains.
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.
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 dynamic problem for a system coupled to a reservoir possessing a dense discrete spectrum of states has been analytically solved under two simplifying assumptions proposed by Zwanzig [15], according to which the reservoir spectrum is equidistant and all the system-reservoir coupling matrix elements are identical (i.e., independent of reservoir states). It is demonstrated that a multicomponent Loschmidt echo arises in each recurrence cycles, the number of components being equal to the cycle number. At a certain critical cycle number, the components of neighboring cycles exhibit mixing. As a result, the dynamics of the system transforms from a regular to stochastic-like dynamics, in which an arbitrarily small coarse graining (inherent in any real system) of the results of measurements or uncertainty in the initial conditions leads to (i) the loss of one-to-one correspondence between the discrete spectrum of eigenvalues and the state of the system and (ii) the loss of invariance with respect to the time reversal. Interrelation between the mixing of cycles with the entanglement of trajectories, on the one hand, and the overlap of resonances in classical systems with mixing, on the other hand, is discussed. The properties of the proposed model are consistent with a variety of the kinetic regimes of vibrational relaxation (from exponential decay to irregular, weakly damping oscillations) observed in various objects. Common features are average distances between neighboring levels on the order of 1–10 cm −1 and recurrence cycles on a time scale of 10 –13 –10 −11 s, which is studied using femtosecond spectroscopy techniques.
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).
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 wave function temporal evolution on the one-dimensional (1D) lattice is considered in the tight-binding approximation.The lattice consists of N equal sites and one impurity site (donor).The donor differs from other lattice sites by the on-site electron energy E and the intersite coupling C. The moving wave packet is formed from the wave function initially localized on the donor.The exact solution for the wave packet velocity and the shape is derived at different values E and C. The velocity has the maximal possible group velocity v = 2.The wave packet width grows with time ∼ t 1/3 and its amplitude decreases ∼ t -1/3 .The wave packet reflects multiply from the lattice ends.Analytical expressions for the wave packet front propagation and recurrence are in good agreement with numeric simulations.