Radiative transitions are quantum-state transitions in matter quantum systems (such as atoms， ions， and molecules) caused by their interaction with the electromagnetic field， and accompanied by the emission or absorption of photons.Their theoretical description involves physical theories including quantum mechanics and quantum electrodynamics， as well as mathematical tools such as spherical tensors and group theory.Focusing on radiative transitions of doped ions in solids， this paper summarizes earlier related theories and aims to concisely introduce fundamental theories and mathematical expressions while maintaining rigor， and to clearly describe the underlying physical pictures and mechanisms.The topics covered include atomic quantum states， the quantized electromagnetic field， multipole radiative transitions and selection rules， stimulated absorption， stimulated emission and spontaneous emission， transition probability and excited-state lifetimes.The article also discusses f-f and 4f-5d transitions of rare-earth ions and dd transitions of transition-metal ions， involving Judd -Ofelt theory， crystal-field theory， electronvibration coupling， and the Dorenbos model， as well as statistical analysis， machine learning， and firstprinciples methods.This work may provide a theoretical reference for the study of rare-earth-and transition-metaldoped luminescent materials.Keywords： radiative transition； theory； physical picture； f-f transition； d-d transition； 4f-5d transition 文章编号： 1000-7032(XXXX)XX
Radiative transitions are quantum-state transitions in matter quantum systems (such as atoms， ions， and molecules) caused by their interaction with the electromagnetic field， and accompanied by the emission or absorption of photons.Their theoretical description involves physical theories including quantum mechanics and quantum electrodynamics， as well as mathematical tools such as spherical tensors and group theory.Focusing on radiative transitions of doped ions in solids， this paper summarizes earlier related theories and aims to concisely introduce fundamental theories and mathematical expressions while maintaining rigor， and to clearly describe the underlying physical pictures and mechanisms.The topics covered include atomic quantum states， the quantized electromagnetic field， multipole radiative transitions and selection rules， stimulated absorption， stimulated emission and spontaneous emission， transition probability and excited-state lifetimes.The article also discusses f-f and 4f-5d transitions of rare-earth ions and dd transitions of transition-metal ions， involving Judd -Ofelt theory， crystal-field theory， electronvibration coupling， and the Dorenbos model， as well as statistical analysis， machine learning， and firstprinciples methods.This work may provide a theoretical reference for the study of rare-earth-and transition-metaldoped luminescent materials.Keywords： radiative transition； theory； physical picture； f-f transition； d-d transition； 4f-5d transition 文章编号： 1000-7032(XXXX)XX
So far we have treated the energy levels of an atomic system as stable states with infinite lifetimes. The presence of an electromagnetic field changes this picture. Absorption of photons will excite atoms and ions to higher levels, while stimulated emission will make excited ones decay. Einstein (1917) showed, using purely statistical arguments, that an excited ion will decay through spontaneous emission in the absence of an electromagnetic field. This process can also be derived by using a rigorous quantum electrodynamic treatment, where the field is quantized. In this chapter we start by discussing transitions between atomic levels in a general sense, postulating the operators responsible for the decay. After the first few sections we will concentrate on the most important few multipoles or terms in the expansion of the electromagnetic field. We will introduce a number of different properties describing the transition, and eventually arrive at the measurable transition rate and, directly linked to it, the lifetime of an excited state. We will start, however, with the most basic property, the component strength. Our aim is to arrive at computationally useful expressions as soon as possible. For a more thorough treatment of the theory of radiative transitions we refer to the book by Sobelman (1972). For a brief review of the many factors affecting spectra of atoms, see Martin and Wiese (1996) .
Radiation can change the energy state of matter via three optical processes: spontaneous emission, absorption and stimulated emission. In spontaneous emission, an excited atomic or molecular state decays to a lower energy state with the emission of a photon of energy equal to the difference in the quantum state energies. Photon absorption is the reverse process, with a photon causing excitation from a lower to an excited quantum state. Stimulated emission was first proposed by Einstein in a paper published in 1917. He attempted to balance spontaneous emission and photon absorption, but could not get the correct balance without the postulated process of stimulated emission (see Section 4.2). With stimulated emission, an excited quantum state is stimulated to decay to a lower quantum state by an impinging photon. The existing photon survives with another identical photon being created (so that energy is conserved). The rates at which radiative transitions occur can be calculated using quantum mechanics. The time-dependent Schrodinger equation is used with the system wavefunction comprising time-varying linear combinations of the two wavefunctions for the lower and upper quantum states. In semi-classical treatments, an atom is treated quantum mechanically with the radiation field treated classically. There is a perturbation in energy associated with, say, the electric field of the radiation interacting with the electric dipole of the atom, though other interactions can be significant if the electric dipole interaction energy is small. In absorption, for example, a differential equation representing the change in ‘weighting’ of the wavefunction from the lower to upper state is obtained. A ‘time constant’ for the speed of change represents the rate of the radiative process. We examine the quantum mechanical nature of radiation absorption in Section 10.1 before discussing (Section 10.3) another important parameter arising with radiative transitions between discrete bound quantum states: the lineshape function. Quantum Theory of the Atom–Radiation Interaction An expression for the Einstein B-coefficient for photo-absorption is derived using quantum mechanics in this section. Einstein determined the detailed balance relationship between the rates of spontaneous emission, photo-absorption and stimulated emission when light interacts with an atom by considering an atomic system of two energy levels which are in equilibrium with a black-body radiation field. We use a semi-classical treatment where the atom is treated quantum mechanically and the radiation field is treated as a classical oscillating electric field.
Abstract The quantum electrodynamic theory, based on the quantization of the electromagnetic field, introduces the concept of photon and the related photon creation operator, photon annihilation operator, and photon number operator. It is used to describe stimulated Raman scattering, stimulated Kerr scattering, and various multiphoton excitation processes. Within this theoretical regime the light (as a photon field) and molecules are treated as a combined quantum mechanical system. The light emission or absorption is always accompanied by the quantum transition of the whole system from its initial eigenstate to the final eigenstate. The molecular emission or absorption probability rate is determined by the corresponding transition matrix elements of the interaction Hamiltonian operator.
Introduction The preceding chapters have focused on atomic transitions induced by applied radiation. That is, there is an optical field illuminating the atoms, and their response is calculated. It is implicitly assumed that an excited atom left alone will spontaneously return to the ground state, and conserve energy by emitting light that satisfies E 2 − E 1 = ħ ω 21 in accordance with the Planck and Bohr pictures. But this spontaneous emission process is not addressed quantitatively in these earlier chapters. Spontaneous emission is one of the most pervasive phenomena of atomic physics, and yet its origins remain among the least well-understood. The number of misconceptions is enormous, and they are to be found in textbooks, journal articles, and lecture notes. Because the natural decay of an excited atom adds energy to what is usually an empty mode of the electromagnetic field, the process is fundamentally quantum mechanical. Classical or even semi-classical descriptions cannot be assured to give correct answers. This is not to say that such discussion is to be avoided, but only that caution is needed in interpreting the results. Toward the end of the nineteenth century, many experimental results made it clear that classical mechanics needed to be supplemented by new theories. The first venture into the new physics was Planck's hypothesis that the energy of classical radiating oscillators like those discussed in Chap. 1 would have to be quantized into integer multiples of ħ ω. This notion led to his famous formula for the spectrum of thermal radiation from a non-reflective object (black body), and this formula describes a radiation field in thermodynamic equilibrium with its environment. The result of Planck's hypothesis in the context of thermal equilibrium plays a vital role in the discussion of spontaneous emission. Einstein A - and B -coefficients Soon after Bohr proposed a model of atomic structure consisting of discrete energy levels, connected by radiation whose energy satisfied Δ E = ħω when atoms made transition between them, Einstein published the first serious attempt to connect the absorption and emission processes. Absorption, he reasoned, could occur only in the presence of applied radiation, whereas spontaneous decay occurred without the application of any field.
We treat the interaction between an electromagnetic radiation bath and a material system in the semi-classical picture: the radiation is treated according to the Maxwell equations, but the process of emission/absorption is described through the concept of a photon; on the other hand, the material system is modelled according to quantum mechanics, assuming a discrete two-level energy spectrum. This very simple model allows one to elaborate the elementary theory of the absorption/emission coefficients, both for the spontaneous and for the stimulated processes which will be described within the electric dipole approximation. Selection rules for allowed transitions are eventually obtained and the nature of high-order transition is briefly outlined. Finally, a qualitative description of the light amplification by stimulated emission of radiation is presented.
Introduction Until now, our discussion of the interaction between radiation and matter has concentrated only on the spectral aspects of radiation. The results could determine the wavelengths for absorption and emission or the selection rules for such transitions, but could not be used to determine the actual extent of emission or absorption. These too are important considerations which are needed to fully quantify radiative energy transfer. Unfortunately, none of the classical theories can predict the extent of emission from an excited medium, or even the extent of absorption. Although the discussion in Section 4.9 (on the propagation of electromagnetic waves through lossy media) touched briefly on the concept of attenuation by absorption, it failed to show the reasons for the spectral properties of the absorption or to accurately predict its extent. We will see later that the classical results are useful only as a benchmark against which the actual absorber is compared. The objective of this chapter is therefore to present an introduction to quantum mechanical processes that control the emission and absorption by microscopic systems consisting of atoms and molecules. The results will then be used to predict the extent of emission by media when excited by an external energy source and to evaluate the absorption of incident radiation. It is now well recognized that all emission or absorption processes are the result of transitions between quantum mechanical energy levels.