In a generic quantum mechanical description of a molecule interacting with its thermal environment, the molecule is represented as a few level system (in the simplest description just two, for example, ground and excited states) and the environment is often modeled as a bath of harmonic oscillators. The resulting theoretical framework is known as the spin–boson model, a term that seems to have emerged in the Kondo problem literature (which deals with the behavior of magnetic impurities in metals) during the 1960s, but is now used in a much broader context. Indeed, it has become one of the central models of theoretical physics, with applications in physics, chemistry, and biology that range far beyond the subject of this book. Transitions between molecular electronic states coupled to nuclear vibrations, environmental phonons, and photon modes of the radiation field fall within this class of problems. The present chapter discusses this model and some of its mathematical implications. The reader may note that some of the subjects discussed in Chapter 9 are reiterated here in this more general framework. In Sections 2.2 and 2.9 we have discussed the dynamics of the two-level system and of the harmonic oscillator, respectively. These exactly soluble models are often used as prototypes of important classes of physical system. The harmonic oscillator is an exact model for a mode of the radiation field and provides good starting points for describing nuclear motions in molecules and in solid environments. It can also describe the short-time dynamics of liquid environments via the instantaneous normal mode approach. In fact, many linear response treatments in both classical and quantum dynamics lead to harmonic oscillator models: Linear response implies that forces responsible for the return of a system to equilibrium depend linearly on the deviation from equilibrium—a harmonic oscillator property! We will see a specific example of this phenomenology in our discussion of dielectric response in Section 16.9.
In a generic quantum mechanical description of a molecule interacting with its thermal environment, the molecule is represented as a few level system (in the simplest description just two, for example, ground and excited states) and the environment is often modeled as a bath of harmonic oscillators. The resulting theoretical framework is known as the spin–boson model, a term that seems to have emerged in the Kondo problem literature (which deals with the behavior of magnetic impurities in metals) during the 1960s, but is now used in a much broader context. Indeed, it has become one of the central models of theoretical physics, with applications in physics, chemistry, and biology that range far beyond the subject of this book. Transitions between molecular electronic states coupled to nuclear vibrations, environmental phonons, and photon modes of the radiation field fall within this class of problems. The present chapter discusses this model and some of its mathematical implications. The reader may note that some of the subjects discussed in Chapter 9 are reiterated here in this more general framework. In Sections 2.2 and 2.9 we have discussed the dynamics of the two-level system and of the harmonic oscillator, respectively. These exactly soluble models are often used as prototypes of important classes of physical system. The harmonic oscillator is an exact model for a mode of the radiation field and provides good starting points for describing nuclear motions in molecules and in solid environments. It can also describe the short-time dynamics of liquid environments via the instantaneous normal mode approach. In fact, many linear response treatments in both classical and quantum dynamics lead to harmonic oscillator models: Linear response implies that forces responsible for the return of a system to equilibrium depend linearly on the deviation from equilibrium—a harmonic oscillator property! We will see a specific example of this phenomenology in our discussion of dielectric response in Section 16.9.
The quantum dynamics of mesoscopic or macroscopic systems is always complicated by their coupling to many `environmental' modes. At low T these environmental effects are dominated by localized modes, such as nuclear and paramagnetic spins, and defects (which also dominate the entropy and specific heat). This environment, at low energies, maps onto a `spin bath' model. This contrasts with `oscillator bath' models (originated by Feynman and Vernon) which describe delocalized environmental modes such as electrons, phonons, photons, magnons, etc. The couplings to N spin bath modes are independent of N (rather than the ~O(1/( N ) 1/2 ) dependence typical of oscillator baths), and often strong. One cannot in general map a spin bath to an oscillator bath (or vice versa); they constitute distinct `universality classes' of quantum environment. We show how the mapping to spin bath models is made, and then discuss several examples in detail, including moving particles, magnetic solitons, nanomagnets, and SQUIDs, coupled to nuclear and paramagnetic spin environments. We then focus on the `central spin' model, which couples a central two-level system to a background spin bath. It is the spin bath analogue of the famous `spin-boson' oscillator model, and describes, e.g., the tunnelling dynamics of nanoscopic and mesoscopic magnets and superconductors. We show how to average over (or `integrate out') spin bath modes, using an operator instanton technique, to find the central spin dynamics. The formal manouevres involve four separate averages - each average corresponds physically to a different `decoherence' mechanism acting on the central spin dynamics. Each environmental spin has its own topological `spin phase', which by interacting with the phase of the central system, decoheres it - this can happen even without dissipation. We give analytic results for the central spin correlation functions, under various conditions. We then describe the application of this theory to magnetic and superconducting systems. Particular attention is given to recent work on tunnelling magnetic macromolecules, where the role of the nuclear spin bath in controlling the tunnelling is very clear; we also discuss other magnetic systems in the quantum regime, and the influence of nuclear and paramagnetic spins on flux dynamics in SQUIDs. Finally, we discuss decoherence mechanisms and coherence experiments in superconductors and magnets. We show that a spin bath environment causes decoherence even in the T 0 limit. Control of this decoherence will be essential in the effort to construct `qubits' for quantum computers.
A method for describing a boson system interacting with an external harmonic oscillator, which was proposed recently by the present authors, is extended to the case of a statistically mixed state. The basic idea comes from the su(2, 1)-boson model, the general form of which was recently investigated by the present authors. In terms of the interweaving of the phase space doubling and the su(1, 1)-spin-like behavior in the su(2)-spin system, the extension is performed in the framework of a canonical form of classical mechanics. The results obtained with regard to the present idea are interpreted from various viewpoints, for example, in relation to linear response theory of non-equilibrium statistical mechanics.
In phenomenological descriptions of nuclear vibrations a close connection is implied or expressed between the most-collective transition operator and the harmonic-oscillator (boson) variables which are introduced to describe the collective motion. With the help of a widely used example - the monopole vibration model of Meshkov, Lipkin, and Glick - it is shown how this relationship suggests, for the microscopic case, a new and flexible class of boson representations. As shown, these are capable of yielding accurate descriptions of the system not only in the extremes of weak and strong coupling, but in the usually more inaccessible intermediate regions as well.
Mechanical motions of atoms near their equilibrium geometry are approximated by a universal mapping on a collection of independent harmonic oscillators. The respective frequencies are characteristic to the material, for example, lattice phonons or molecular vibrations. The quantum description of atomic motions involves the solution of the Schrödinger equation for the harmonic oscillator in the space of proper wave functions. The energy levels obtained are shown to be equally spaced where the level spacing is proportional to the oscillator frequency. The stationary solutions are identified in terms of Hermite polynomials, demonstrating remarkable differences from the classical harmonic oscillator. The importance of the zero-point energy is emphasized in the context of the stability of chemical bonds, where the Harmonic approximation is shown to be reasonably valid for typical interatomic bonds in standard thermal conditions. This explains the relevance of the harmonic approximation for analyzing the absorption spectrum of infrared radiation by molecules.
Ground states of a spin-boson Hamiltonian, describing one two-level system (a spin) coupled to infinitely many harmonic oscillators (bosons), are studied. This spin-boson Hamiltonian is a prototype for the description of a ‘‘small’’ system (e.g., a molecule) coupled to its environment. The respective ground-state vector(s) are approximated by a linear combination of two coherent-state vectors corresponding to the two levels of the spin. Interest concentrates mainly on phase-transition phenomena (generation of superselection rules) in case the parameters of the Hamiltonian (level splitting of the spin, frequencies of the field modes, and coupling constants) exhibit an infrared singularity. The resulting phase diagrams are shown to satisfy reasonably well the rigorous bounds derived by Spohn, and in particular distinguish between the superohmic, ohmic, and subohmic regime in the sense of Leggett. Nevertheless, the approximation method used is simple enough so that everything can be explicitly calculated. Former results by Pfeifer as well as results by Emery and Luther, Zwerger and Harris and Silbey are extended and discussed.
The thermodynamics of a two-level system coupled to a boson field is investigated by means of a functional-integral method. The model can be used to describe the motion of a small polaron between two sites on a molecule, or a spin-1/2 magnetic moment coupled to a phonon bath. The model is also relevant to the problem of dissipation in macroscopic quantum phenomena. We use a functional-integral method to investigate a two-level electronic system coupled linearly to a harmonic oscillator. The density matrix is cast as a functional integral over paths obeying one-sided boundary conditions at either 0 or \ensuremath{\beta}=1/kBT. The integration variables are c numbers for the oscillator and Grassmann numbers for the electrons. The oscillator variables are integrated out, leaving an effective density matrix for the electrons containing retarded interactions. The partition function is then calculated up to second order of an expansion about the exact fermionic classical paths. Then, the free energy, specific heat, and average hopping energy are obtained. We find that the most significant reduction in the hopping energy is manifested at intermediate temperatures.