Coherent states molecular photonics, quantum

In the discussion of the experimental approaches to study molecular resonances, the quantum theory of photon wave packet scattering forms the natural framework. It is thus necessary to recall some of the main features of wave packet scattering (Messiah, 1965 Newton, 1966 Goldberger and Watson, 1965a) with special reference to photophysical phenomena (Shore, 1967). We begin with a brief review of the basic concepts in the formal description of time evolution. Then we consider more in detail the process of scattering of a coherent photon wave packet by a molecule. The expressions for the basic experimental observables are derived, with special emphasis on time-resolved studies. Detection is assumed to take place under short time conditions, in a lateral, nonforward direction so that no coherence of the photon states scattered by different molecules must be considered. 

Photons in quantum optical cavities also constitute excellent qubit candidates [52]. Resonant coupling of atoms with a single mode of the radiation field was experimentally achieved 25 years ago [53], and eventually the coherent coupling of quantum optical cavities with atoms or (simple) molecules was suggested as a means to achieve stable quantum memories in a hybrid quantum processor [54]. There might be a role to play for molecular spin qubits in this kind of hybrid quantum devices that combine solid-state with flying qubits. 

The first volume contained nine state-of-the-art chapters on fundamental aspects, on formalism, and on a variety of applications. The various discussions employ both stationary and time-dependent frameworks, with Hermitian and non-Hermitian Hamiltonian constructions. A variety of formal and computational results address themes from quantum and statistical mechanics to the detailed analysis of time evolution of material or photon wave packets, from the difficult problem of combining advanced many-electron methods with properties of field-free and field-induced resonances to the dynamics of molecular processes and coherence effects in strong electromagnetic fields and strong laser pulses, from portrayals of novel phase space approaches of quantum reactive scattering to aspects of recent developments related to quantum information processing. 

The spectrum of the excitations is shown in Fig. 10.5 for 2 A = 80 meV. The dashed lines show the uncoupled molecular excitons and photons, and the solid lines show the coherent part of the spectrum with well-defined wavevector. The crosses show the end-points of the spectrum of excitations for which q is a good quantum number. The spectrum of incoherent (weakly coupled to light) states is shown by a broadened line centered at the energy Eq. It follows from the expression for the dielectric tensor that this spectrum is the same as the spectrum of out-of-cavity organics. The spectrum of absorption as well as the dielectric tensor depend on temperature. This means that in the calculation of the temperature dependence of the polariton spectrum we have to use the temperature dependence of the resonance frequency Eo as well as the temperature dependence of 7 determining the width of the absorption maximum. However, the spectrum of emission of local states which pump polariton states can be different from the spectrum of absorption. The Stokes shift in many cases... 

In its broadest sense, spectroscopy is concerned with interactions between light and matter. Since light consists of electromagnetic waves, this chapter begins with classical and quantum mechanical treatments of molecules subjected to static (time-independent) electric fields. Our discussion identifies the molecular properties that control interactions with electric fields the electric multipole moments and the electric polarizability. Time-dependent electromagnetic waves are then described classically using vector and scalar potentials for the associated electric and magnetic fields E and B, and the classical Hamiltonian is obtained for a molecule in the presence of these potentials. Quantum mechanical time-dependent perturbation theory is finally used to extract probabilities of transitions between molecular states. This powerful formalism not only covers the full array of multipole interactions that can cause spectroscopic transitions, but also reveals the hierarchies of multiphoton transitions that can occur. This chapter thus establishes a framework for multiphoton spectroscopies (e.g., Raman spectroscopy and coherent anti-Stokes Raman spectroscopy, which are discussed in Chapters 10 and 11) as well as for the one-photon spectroscopies that are described in most of this book. 

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