Anisotropy of angular momenta: ideas and methods The fundamental idea forming the basis of early quantum theory was the quantization of the angular momentum of the atom, which, at a later stage, assumed the form of the Bohr–Sommerfeld quantization rule [360], namely ∲ pdq = n ℏ where p and q are the generalized momentum and coordinate. This concept has retained its physical meaning in modern-day quantum mechanics [371, 372]. In the course of the further development of quantum mechanical concepts it became increasingly clear that in the theory of atoms and molecules the angular momentum is a ‘dominant’ notion, the fundamental significance of which is in no small degree connected with its dimension of action, which coincides with that of Planck's constant ℏ. In the interaction between particles and a directed beam of photons the angular momentum of the system is conserved, thus forming the basis for the optical method of producing spatial anisotropy of the distribution of the angular momenta of the ensemble of particles, i.e. its optical polarization . In terms of quantum concepts, spatial anisotropy means that in an ensemble of particles a non-equilibrium population of magnetic sublevels m j of angular momenta is created. We make a distinction between the alignment of momenta, for instance in the absorption of linear polarized light, when there is no difference between the population of ± m j -sublevels, and orientation , when such a difference exists. Anisotropic distribution of angular momenta in an excited state, as produced in absorption, manifests itself directly in the polarization of fluorescence. It is rather likely that understanding of the anisotropic distribution of the angular momenta of atoms was enhanced by Hanle's [184] discovery in 1924.
Anisotropy of angular momenta: ideas and methods The fundamental idea forming the basis of early quantum theory was the quantization of the angular momentum of the atom, which, at a later stage, assumed the form of the Bohr–Sommerfeld quantization rule [360], namely ∲ pdq = n ℏ where p and q are the generalized momentum and coordinate. This concept has retained its physical meaning in modern-day quantum mechanics [371, 372]. In the course of the further development of quantum mechanical concepts it became increasingly clear that in the theory of atoms and molecules the angular momentum is a ‘dominant’ notion, the fundamental significance of which is in no small degree connected with its dimension of action, which coincides with that of Planck's constant ℏ. In the interaction between particles and a directed beam of photons the angular momentum of the system is conserved, thus forming the basis for the optical method of producing spatial anisotropy of the distribution of the angular momenta of the ensemble of particles, i.e. its optical polarization . In terms of quantum concepts, spatial anisotropy means that in an ensemble of particles a non-equilibrium population of magnetic sublevels m j of angular momenta is created. We make a distinction between the alignment of momenta, for instance in the absorption of linear polarized light, when there is no difference between the population of ± m j -sublevels, and orientation , when such a difference exists. Anisotropic distribution of angular momenta in an excited state, as produced in absorption, manifests itself directly in the polarization of fluorescence. It is rather likely that understanding of the anisotropic distribution of the angular momenta of atoms was enhanced by Hanle's [184] discovery in 1924.
We know now how alignment and orientation of angular momenta arise in the excited state as a result of optical excitation from the primarily isotropic distribution of the ensemble of angular momenta. This phenomenon reflects, in essence, the anisotropy of absorption probability G (θ,ϕ). Since spatial structures of the type shown in Fig. 2.2 appear in the excited state the same structure must be ‘eaten out’ from the angular momentum distribution in the ground (initial) state. If the gap created is not closed quickly enough, the ensemble of the remaining angular momenta of the absorbing molecules in the ground state must necessarily also be polarized. If, from another point of view, fluorescent decay leads to a considerable population of the ground state level c, (see, e.g., Fig. 1.2), then molecules on this level may exhibit angular momenta polarization, being particularly noticeable for thermally unpopulated, high lying levels. In the present chapter we intend to discuss the conditions necessary for the creation of ground state angular momenta polarization, the possibilities of its experimental observation, and to develop the theoretical description of broad line radiation interaction with molecules further. Angular momenta polarization via depopulation For many years there existed the widespread opinion that in molecules we obtain an anisotropic distribution of angular momenta only in the excited state in the absorption process, whilst in the ground state isotropy is conserved [124]. This conjecture is based essentially on the assumption of the existence of a so-called ‘weak’ excitation. At first sight it may appear, for instance, from Eq. (2.20) that, as is usual in non-linear spectroscopy, such an admission is correct if condition Γ p /Γ ≫ 1 is valid.
Quantization of spin and orbital angular momenta in standard quantum mechanics is rooted in the fundamental rotational symmetry of space in conjunction with the results of experiments on atomic and subatomic particles conducted with the Stern-Gerlach apparatus. We explain some of the most important features of spin and orbital angular momenta as inescapable consequences of elementary Stern-Gerlach experiments viewed in light of the rotational symmetry of space. The rotation operator is first derived for spin-½ particles, then extended to spin-1 particles by treating the case of a hydrogen atom in its ground state, where the spin of the proton combines with that of the electron to create a spin-1 triplet state. Along the way, we examine the evolution of a particle’s spin state under an applied magnetic field, where the interaction energy arises from the existence of a magnetic dipole moment for each particle in proportion to its spin angular momentum. Whereas a constant magnetic field B0 causes the particle’s magnetic moment to gyrate around the direction of B0, it will be seen that the presence of a small oscillating magnetic field perpendicular to B0 brings about the so-called Rabi oscillations, which involve periodic flippings of the particle’s spin orientation. In the case of a hydrogen atom in its ground state, the interaction between the magnetic dipole moments of the proton and the electron splits the ground state between a lower energy singlet having a net angular momentum of zero (spin-0 state), and a higher energy triplet having a total angular momentum of ħ (spin-1 state). This hyperfine splitting is the source of the well-known 21-cm line observed in the spectrum of the hydrogen atom, which arises from transitions between the atom’s singlet and triplet states. In the final section, we put forward an argument (originally made by Richard Feynman) that ties the rotational symmetry of space to the conservation of angular momentum in quantum mechanics. The argument is, in fact, quite general, enabling one to deduce other conservation laws from various inherent symmetries of quantum mechanical systems.
THE QUANTUM THEORY OF ANGULAR MOMENTUM began with Bohr’s enunciation of the rules for the quantization of orbital angular momentum in 1913, and the refinement of these rules by Sommerfeld [ 1 ] and Landé [ 2 ] within the framework of the old quantum theory. A basic result for angular momentum in modern quantum theory, which we call The First Fundamental Result, was given in the third foundational paper in 1926 by Born, Heisenberg, and Jordan [ 3 ], who not only gave the basic commutation relations for the components of the total angular momentum J, but all finite-dimensional Hermitian matrix representations of these components. Dirac [ 4 ] simultaneously deduced these basic commutation relations using his algebraic approach to quantum mechanics, and later gave a marvelously brief derivation of their matrix representations in his book [ 5 ]. Further developments, including the famous Pauli matrices and results relating to angular momentum selection rules for transitions in atomic systems, are given in the papers by Heisenberg and Jordan [ 6 ], Pauli [ 7 ], and Güttinger and Pauli [ 8 ]. These works, and the books by Born and Jordan [ 9 ] and Condon and Shortley [ 10 ], fixed the framework for much of the developments in angular momentum theory, which was hardly distinguishable from the general quantum theory in the context of which it was developed for the purpose of giving a consistent description of the spectra of atoms. Little emphasis was given to the universal and distinctive role of symmetry.
The Wigner representation of angular-momentum orientation in the classical limit on $J\ensuremath{\gg}1$ has been used to derive an equation of angular-momentum motion in the case of a closed two-level system interacting with an arbitrary polarized radiation. This equation enables us to carry out a theoretical analysis of angular-momentum motion and consider final states of the quantum system for all types of dipole transitions. We have found that in the case of a zero magnetic field in the final state of the system with $\stackrel{\ensuremath{\rightarrow}}{J}J$ or $\stackrel{\ensuremath{\rightarrow}}{J}J+1$ optical transition, the angular momentum is directed along or opposite to the wave vector of the radiation depending on the sign of the polarization ellipsity, while for a linear polarization the angular momentum is isotropically distributed on the plane orthogonal to the polarization vector. For the $\stackrel{\ensuremath{\rightarrow}}{J}J\ensuremath{-}1$ transition two directions of angular momentum are possible in the final state. These directions are determined by the ellipsity of polarization. The spatial size of the final distribution of the angular momentum has been defined by the quantum uncertainty, 1/J, of the angular-momentum orientation. In the case of the $\stackrel{\ensuremath{\rightarrow}}{J}J\ensuremath{-}1$ or $\stackrel{\ensuremath{\rightarrow}}{J}J,$ transition particles come into ``dark'' states while for the $\stackrel{\ensuremath{\rightarrow}}{J}J+1$ transition they occupy the ``brightest'' state. In the presence of a nonzero magnetic field, particles with $\stackrel{\ensuremath{\rightarrow}}{J}J$ transition have in the final state only one angular-momentum orientation, i.e., along or opposite to the direction of the magnetic field depending on the polarization ellipsity sign. For the $\stackrel{\ensuremath{\rightarrow}}{J}J+1$ transition both directions are possible, i.e., along and opposite to the magnetic field. In the case of the $\stackrel{\ensuremath{\rightarrow}}{J}J\ensuremath{-}1$ transition the directions of the angular momentum form a cone around the magnetic field.
Abstract A century ago Einstein introduced the notion of the linear momentum of a photon, h k, and analyzed its transfer to an atom (and back) in the establishment of thermodynamic equilibrium between black-body radiation and matter. In addition to a linear momentum, the photon also possesses an angular momentum, ħ, directed parallel (or antiparallel) to its propagation direction (the OZ axis in Fig. 4.1), depending on its polarization direction (left- or right-handed). This angular momentum is due to the spin of the photon, equal to 1. Half a century later, Kastler (1950) considered the use of the transfer of the angular momentum of a polarized photon to the angular momentum of an atom as a method of optical orientation of atoms. In essence, this was the first method to control atomic motion by means of low-intensity light, developed even before the advent of the laser; it which found widespread application in investigating and then using spin polarization effects in atomic physics. But even after lasers had made their appearance, the method of optical orientation of atoms (or pumping of certain magnetic sublevels in atoms) proved very important, specifically in the laser cooling of atoms (Chapter 5).
Angular momentum is essential to any advanced discussion of magnetic resonance spectroscopy. A brief history of the modern sub-atomic particle-spin concept is presented. The origin of the spin-1/2 angular momentum quantum number is detailed and angular momentum operators are constructed for spin-1/2 nuclei using the postulates of quantum mechanics which are then used to produce a set of very useful eigenvalue formulas. Angular momentum operators in spherical coordinate form are developed and operator matrices are constructed from Cartesian operators. The time-evolution of these operators is of much interest in later chapters and is explored in some detail here.