The time evolution of an unstable quantum system in terms of the dynamical semigroup is described. Using the canonical decomposition theorem, the evolution semigroup is uniquely split into unitary and completely nonunitary parts. This feature provides a natural superselection principle. An association is then made of the evolution of the steady-state density matrix with the unitary part and that of the decaying-state density matrix with the completely nonunitary part. Thus the reversible dynamics goes with the unitary evolution and the irreversible one with the completely nonunitary evolution. A discussion of the von Neumann entropy of this system is also presented. It is shown that for long times, this entropy settles to a constant value different from the initial entropy. A simple example of an exponentially decaying state is discussed.
The time evolution of an unstable quantum system in terms of the dynamical semigroup is described. Using the canonical decomposition theorem, the evolution semigroup is uniquely split into unitary and completely nonunitary parts. This feature provides a natural superselection principle. An association is then made of the evolution of the steady-state density matrix with the unitary part and that of the decaying-state density matrix with the completely nonunitary part. Thus the reversible dynamics goes with the unitary evolution and the irreversible one with the completely nonunitary evolution. A discussion of the von Neumann entropy of this system is also presented. It is shown that for long times, this entropy settles to a constant value different from the initial entropy. A simple example of an exponentially decaying state is discussed.
Each semigroup describing time evolution of an open quantum system on a finite dimensional Hilbert space is related to a special structure of this space. It is shown how the space can be decomposed into orthogonal subspaces: One part is related to decay, some subspaces of the other subspace are ranges of the stationary states. Specialities are highlighted where the complete positivity of evolutions is actually needed for analysis, mainly for evolution of coherence. Decompositions are done the same way for discrete as for continuous time evolutions, but they may show differences: Only for discrete semigroups there may appear cases of sudden decay and of perpetual oscillation. Concluding the analysis, we identify the relation of the state space structure to the processes of decay, decoherence, dissipation and dephasing.
For a quantum state undergoing unitary Schrödinger time evolution, the von Neumann entropy is constant. Yet the second law of thermodynamics, and our experience, show that entropy increases with time. Ingarden introduced the quantum operator entropy, which is the Shannon entropy of the probability distribution for the eigenvalues of a Hermitian operator [R. S. Ingarden, Quantum information theory, Rep. Math. Phys. 10, 43 (1976)RMHPBE0034-487710.1016/0034-4877(76)90005-7]. These entropies characterize the missing information about a particular observable inherent in the quantum state itself. The von Neumann entropy is the quantum operator entropy for the case when the operator is the density matrix. We examine pure state unitary evolution in a simple model system composed of a set of highly interconnected topologically disordered states and a time-independent Hamiltonian. An initially confined state is subject to free expansion into available states. The time development is completely reversible with no loss of quantum information and no course graining is applied. The positional entropy increases in time in a way that is consistent with both the classical statistical mechanical entropy and the second law.
We consider the temporal evolution of the entropy S of an isolated system from an initial non-equilibrium state 2· of entropy S = S i to the equilibrium state of maximum entropy S = S max > S i. The application of usual density matrix theory of quantum mechanics leads us to the surprising result P = dS/dt = 0. The entropy does not change in time. This result is valid in case of the equilibrium state. However it is wrong for a non-equilibrium state, because the entropy of the isolated system could not spontaneously increase from S i to S max by entropy production P > 0. This contradicts the second law of thermodynamics. We avoid this discrepancy by changing from quantum mechanics to quantum thermodynamics. Now the entropy production P = dS/dt and the time t are the relevant observables. In order to treat the temporal development of S and P, we at first prepare an initial state i of entropy production P i at time t < 0. Subsequently at ϑ t ≥ 0 the initial state i interacts with a continuum of final states f, which transfers the entropy production from i to f. The temporal evolution of the entropy production P(t) of our system is treated by means of the time-dependent perturbation theory. For that reason we split the operator of entropy production P = P 0 + W into two parts. The operator P 0 describes the unperturbed basic vectors of entropy production | i > and | f >, while the perturbation operator W determines the interaction between | i > and | f >. We expand the time-dependent state function < t | ψ > of the isolated system into the complete set of stationary eigenvectors | i > and | f > and calculate the time-dependent expansion coefficients c i(t) and c(f, t) by means of the dynamic equation of quantum thermodynamics − i k (d/dt) < t | ψ > = < t | P | ψ >. Here k means the Boltzmann constant, which is characteristic of quantum thermodynamics and represents the atomic entropy unit. The expansion coefficients are given by a system of coupled differential equations, from which we deduce an integral-differential equation for the coefficient c i(t) of the initial state i. Unfortunately it has been impossible to obtain an analytic solution of the complicated equation. However approximations are available. Accordingly, in the vicinity of the equilibrium state, the probability of still finding the initial state i of entropy production P i at time t is given by ω i(t) = | c i(t) |2 = exp (−Lt). The rate constant L ≥ σ depends on the density ρ(P f) of final states f of entropy production P f near by P i, and on the squared modulus of the perturbation matrix elements W if = < i | W | f >, which determines the interaction between | i > and | f >. The entropy production P(t) = P i ω i(t) = P i exp (−ϑLt) of the isolated system decreases exponentially and irreversibly with proceeding time t. Its rate-determining step is the transfer of entropy production from i to f. The integral over the entropy production of the final states f vanishes. Therefore the continuum states f do not contribute to the total entropy production P(t). The temporal evolution of the entropy S(t) can easily be calculated by integration of P(t). In conclusion, the entropy production of a non-equilibrium state is finite P(t) > 0 and only vanishes in the case of the equilibrium state P(∞) = 0. Thus, quantum thermodynamics agrees with the second law of thermodynamics.
For a quantum state undergoing unitary Schrodinger time evolution, the von Neumann entropy is constant. Yet the second law of thermodynamics, and our experience, show that entropy increases with time. Ingarden introduced the quantum operator entropy, which is the Shannon entropy of the probability distribution for the eigenvalues of a Hermitian operator. These entropies characterize the missing information about a particular observable inherent in the quantum state itself. The von Neumann entropy is the quantum operator entropy for the case when the operator is the density matrix. We examine pure state unitary evolution in a simple model system comprised of a set of highly-interconnected topologically disordered states and a time-independent Hamiltonian. An initially confined state is subject to free expansion into available states. The time development is completely reversible with no loss of quantum information and no course graining is applied. The positional entropy increases in time in a way that is consistent with both the classical statistical mechanical entropy and the second law.
The well-known magnetic or optical Bloch equations are extended to the case of unstable systems such as, e.g., spontaneously decaying particles and molecules undergoing chemical reactions or decaying from excited states back to states other than those involved in resonance. The modified equations are derived from a general theory of irreversible processes where quantum Markovian master equations and the corresponding completely positive dynamical semigroups dictate the time evolution of density operators. The results are of particular importance in those situations where decay occurs level-selectively and all relaxation and decay constants are of comparable order of magnitude. The obtained generalized Bloch equations are of direct applicability to problems of time-resolved magnetic or optical resonance spectroscopy.
Basic notions and theWigner–Weisskopf theory Although the notions of bound states, scattering and quantum transitions are well defined in the quantum theory, the description of an unstable system, involved in the process of decay, has remained an outstanding issue for many years. The problem is fundamental, since it concerns the nature of irreversible processes, one of the most important issues in statistical mechanics and the theme that is central to this book. The theory of decay is intimately connected with scattering theory and necessarily contains mathematical ideas and methods. We shall try to explain these points carefully as we get to them. We treat elsewhere in the book the ideas of Boltzmann, Van Hove and Prigogine on irreversible phenomena. The tools that are developed there are basically approximate, although very useful. One can argue that the basic rigorous characteristic of an irreversible process is that, as represented in terms of the evolution of a state in the Hilbert space of the quantum theory, it must be a semigroup. This type of evolution, resulting in an operation Z ( t ) on a state ψ , should satisfy the property Z ( t 2 ) Z ( t 1 ) = Z ( t 1 + t 2 ). (17.1) The argument is as follows. If the system evolves in time t 1 and is stopped, then evolves further at time t 2 , since the process has no memory, the total evolution should be as if the system evolved from the initial state to a state at t 1 + t 2 independently of the fact that it was done in two stages (Piron, 1976). Since the process is irreversible, the operator Z ( t ) may have no inverse. Such an evolution is called a semigroup . As we shall see, it is not possible to obtain such an evolution law in the framework of the standard quantum theory (Horwitz et al. , 1971), but recently much work has been done, and methods have been developed, based on ideas of Sz.-Nagy and Foias (1976), such as the theory of Lax and Phillips (1967) and its extension to the quantum theory (Strauss et al. , 2000) in which semigroup evolution can be achieved.