The work is devoted to the investigation of the influence of a heat bath on the physical processes in a quantum system. We use the density matrix theory as one of the most powerfool tool for investigation of quantum relaxation. In the beginning of the work (chapter 2) we mention and recall the most important steps of derivation of the equation of motion for the reduced density matrix (master equation) for an arbitrary quantum system in diabatic representation interacting with the environment modeled by a set of independent harmonic oscillators. Chapter 3 deals with the question of the border between classical and quantum effects and reports on a study of the environmental influence on the time evolution of a coherent state or the superposition of two coherent states of a harmonic oscillator as a simple system displaying the peculiarities of the transition from quantum to classical regime. Chapters 4 and 5 concern the electron transfer (ET) problem, namely the mathematical description of the ET in molecular zinc-porphyrin-quinone complexes modeling artificial photosynthesis (chapter 4) and photoinduced processes in the porphyrin triad (chapter 5). Each chapter starts with an introduction and ends with a brief summary. The main achievements of the present work are summarized in the Conclusions.
The work is devoted to the investigation of the influence of a heat bath on the physical processes in a quantum system. We use the density matrix theory as one of the most powerfool tool for investigation of quantum relaxation. In the beginning of the work (chapter 2) we mention and recall the most important steps of derivation of the equation of motion for the reduced density matrix (master equation) for an arbitrary quantum system in diabatic representation interacting with the environment modeled by a set of independent harmonic oscillators. Chapter 3 deals with the question of the border between classical and quantum effects and reports on a study of the environmental influence on the time evolution of a coherent state or the superposition of two coherent states of a harmonic oscillator as a simple system displaying the peculiarities of the transition from quantum to classical regime. Chapters 4 and 5 concern the electron transfer (ET) problem, namely the mathematical description of the ET in molecular zinc-porphyrin-quinone complexes modeling artificial photosynthesis (chapter 4) and photoinduced processes in the porphyrin triad (chapter 5). Each chapter starts with an introduction and ends with a brief summary. The main achievements of the present work are summarized in the Conclusions.
In this thesis, the influence of an environment on molecules and, in particular, on the quantum control of such systems is investigated. Different approaches to describe system-bath dynamics are implemented and applied. The inclusion of a dissipation term in the system Hamiltonian leads to energy loss and relaxation to the ground state. As a first application, the isomerisation reaction in an aromatic complex is treated. It is shown that this simple model is able to reproduce results of time-resolved spectroscopic measurements. Next, the influence of noise is investigated. The incorporation of fluctuations reveals that energy is not conserved and coherences are destroyed. As an example, the quantum control of a population transfer in Na2 is examined. The efficiency of control processes is studied in dependence on the strength of the noise and different system-bath couplings. Starting with the unperturbed system, Local Control Theory is applied to construct a field which selectively transfers population into a single excited electronic state. The coupling to the bath is then switched on to monitor the dependence of the coupling strength on the transfer efficiency. The perturbation of the bath effects the Na2 molecule in such a way that potential energy curves and transition dipole moments are distorted. An important result is that already elastic collisions lead to a substantial loss of control efficiency. The most promising approach used in this thesis is the stochastic Schrödinger equation. It is equivalent to the commonly employed descriptions of system-bath dynamics within the reduced density matrix formalism. It includes decoherences and dissipation caused by elastic and inelastic collisions. Our contribution is the incorporation of laser excitation into the kinetic Monte-Carlo scheme. Thus we are able to apply this stochastic approach to the quantum control of population transfer in the sodium dimer. Because within our description it is possible to separate pure dephasing, inelastic transitions, and coherent time-evolution, we can identify the relative influence of these processes on the control efficiency. This leads to a far more physical picture of the basic processes underlying the perturbations of an environment then what a reduced density matrix description can provide. In utilising the stochastic wave function approach instead of the density matrix formalism, the computations are quite efficient. The stochastic Schrödinger equation is realised by N independent runs, where, in our case, an ensemble size of N = 1000 gives converged results. The efficiency of the laser control process is studied as a function of temperature and collision rates. A rise in temperature (or collision rate) reeffects a stronger fluctuation and thus results in a less efficient transfer by the control field. Though the Gaussian fluctuations used here do not strictly represent 'white'- noise, since a deterministic machine is not able to produce uncorrelated random numbers, an acceptable distribution is achieved by simple procedures. An improvement of the here applied algorithms would, for instance, include a more sophisticated sampling of the dephasing rates. Only one example of a control process is studied here and an application of the developed approach to other problems of quantum control is to be performed. This thesis established a systematic approach to understand quantum control in the presence of an environment.
In this chapter we study some properties of systems of coupled quadratic quantum Hamiltonians. The well known example is coupled harmonic oscillators appearing in the Quantum Brownian Motion. An open system is a physical (S) interacting with the environment (E) such that the total system (S∪E) is isolated from the rest of the universe. So we have two independent Hamiltonians H^S, H^E and an interaction V^ between (S) and (E). The main problem discussed for open systems is to understand the dynamical action of the interaction V^ with the environment on the time dependent evolution of (S) which is now irreversible because a part of its energy escapes to the environment. An important physical effect of the interaction of the environment on a quantum system is decoherence which give an explanation for the mechanism driving the quantum-to-classical transition. We restrict ourself to few mathematical problems related with this very active field of research in physics [155, 200, 231, 270]. In a first part we study the purity of a state of (S) (or the linear entropy) in a short time approximation. In a second part we discuss the separability of bipartite systems. In a third part we establish a master equation (or a Fokker-Planck type equation) for the time evolution of the reduced matrix density for coupled quadratic Hamiltonians by a bilinear inter-action. We give an explicit formula for the solution of this master equation so that the time evolution of the reduced density at time t is written as a convolution integral for the reduced density at initial time t0=0, with a Gaussian kernel, for 0≤t<tc where tc∈]0,∞] is a critical time such that reversibility is lost for t>tc if tc<+∞. Some manifestations of decoherence, for t>0 small enough, are proved on our simple model which is similar to a representation of the Schrödinger cat.
This work concerns itself with the exact study of the dynamical properties of two model systems. After a brief summary of theory and concepts previous work is discussed, and this provides the motivation for the formulation of the first model. This quantum mechanical lattice model and some of its equilibrium properties are described in Chapter II. The dynamical problem to be studied is formulated in Chapter III; this is essentially the study of the time evolution (generated by the Hamiltonian) of a finite system at temperature T1 coupled to an infinite copy of itself at a temperature T2 and acting as a heat bath for the system. The problem is solved for the special case, when the coupling as scaled by the parameter γ, takes the value γ = 1. The general case for arbitrary γ values is treated in Chapter IV. It is shown that the system approaches the equilibrium state of the heat bath in a non-exponential manner, provided the spectrum of the Hamiltonian is continuous and does not have a discrete part. This result is in complete accord with the findings of other work summarised in Chapter I. The mixing properties of the model and behaviour of the relaxation rate in the weak coupling limit are studied in Chapter V. The model is shown to fail to behave as a calorimeter and in view of this result the relevance of the concept of mixing to irreversible behaviour is discussed. The main conclusions and results for the model are summarised at the end of Chapter V. The second model discussed, was first introduced by R.J. Glauber to study the dynamics of the Ising chain. The main feature here is that the time evolution is defined through a Master equation, and the associated stochastic operator. It is shown in Chapter VI that exploiting fully the free fermion character of the stochastic operator for the Glauber model, it is possible to provide a simple method to the study of the dynamics of the Ising Chain.
The arguments of Chapter 2, as well as of those of subsequent chapters, have as their foundation the formalism based on the state vector of a system of which the evolution is described by the Schrödinger equation. In fact, such an approach is badly suited to the case in which the coupling between an atom and its environment (for example through collisions with other atoms or spontaneous emission into formerly empty modes of the electromagnetic field) cannot be neglected. If the correlations induced by these interactions between the atom and its environment do not concern us and we are only interested in the evolution of the atom, the formalism of the density matrix must be employed. This provides a description at all times of the state of the atom, although a state vector for the atom alone cannot be defined. In this formalism the effect of the environment on the atom is accounted for by the introduction of suitable relaxation terms (Section 2C.1) in the equation of evolution of the density matrix. An important application of the density matrix is to the case of a two-level atomic system for which the relaxation terms lead to its deexcitation to a level of lower energy. We shall show that in this case the density matrix can be represented by a vector, known as the Bloch vector , which will allow us to give simple geometrical pictures of the evolution of the system.
Abstract This chapter introduces the density operator and the Liouville equation and outlines how reduced dynamical description of open quantum systems naturally leads to the appearance of relaxation processes. (1) The density operator and the quantum Liouville equation (the density matrix for a pure system, statistical mixtures, representations, coherences, thermodynamic equilibrium). (2) An example: The time evolution of a two-level system in the density matrix formalism. (3) Reduced descriptions. (4) Time evolution equations for reduced density operators: The quantum master equation (projection operators, The Nakajima–Zwanzig equation, Derivation of the quantum master equation using the thermal projector, The quantum master equation in the interaction representation, The Markovian limit—the Redfield equation, The secular approximation and the Lindblad equation). (5) The Lindblad equation in the ‘Heisenberg representation’. (6) Relaxation of a two-level system and a harmonic oscillator revisited. (7) The optically driven two-level system in a thermal environment—the Bloch equations. (8) The oscillating dipole model of a two-level molecule. (9) Analogy of a coupled two-level system to a spin ½ system in a magnetic field.
This thesis is concerned with modelling the dynamics of open quantum systems in several different contexts. Of principal interest is the manner in which the environment can modify, or even dominate, a system’s quantum behaviour in order to facilitate the transport of energetic excitations. In the first research chapter, a time-local, non-Markovian quantum master equation is derived in a variationally defined reference frame, for networks of two-level systems coupled to bosonic environments. The predictions of this master equation are then compared with those derived using both weak-coupling and polaron approximations. The variational master equation is found to agree with these standard approaches in their regimes of validity, whilst interpolating between them in intermediate parameter regimes. The second research chapter focusses on the dynamics of a superconducting double quantum dot embedded in a resonant circuit. The device is considered in a regime where the ground state consists of a coherent spatial superposition of a single Cooper pair, which can be excited by a variety of interactions with the environment. The relevant transition rates are calculated and the processes responsible are identified. A numerical simulation of the system is then used to explain experimental data, and show that for certain parameters a significant fraction of excitations occur via absorption of photons from the environment. The final chapter considers a model for an olfactory receptor, in which odorant molecules are recognised by their vibrational modes. Electron transfer occurs in the receptor, dependent on the presence of a vibrational mode of the right frequency. A quantum master equation for the system is derived, and the resulting dynamics is compared to earlier semi-classical treatments. The behaviour of the receptor is found to be sensitive not only to the frequency of the vibrational mode, but also to the character of the surrounding environment. Increased dissipation on the odorant mode, as well as the presence of higher frequencies in the environment is found to improve the frequency resolution of the receptor.