Fundamentals of Diatomic Molecular Spectroscopy

The interpretation of optical spectra requires thorough comprehension of quantum mechanics, especially understanding the concept of angular momentum operators. Suppose now that a transformation from laboratory-fixed to molecule-attached coordinates, by invoking the correspondence principle, induces reversed angular momentum operator identities. However, the foundations of quantum mechanics and the mathematical implementation of specific symmetries assert that reversal of motion or time reversal includes complex conjugation as part of anti-unitary operation. Quantum theory contraindicates sign changes of the fundamental angular momentum algebra. Reversed angular momentum sign changes are of heuristic nature and are actually not needed in analysis of diatomic spectra. This work addresses sustenance of usual angular momentum theory, including presentation of straightforward proofs leading to falsification of the occurrence of reversed angular momentum identities. This review also summarises aspects of a consistent implementation of quantum mechanics for spectroscopy with selected diatomic molecules of interest in astrophysics and in engineering applications.

Solvable Model of a Generic Driven Mixture of Trapped Bose–Einstein Condensates and Properties of a Many-Boson Floquet State at the Limit of an Infinite Number of Particles

A solvable model of a periodically driven trapped mixture of Bose–Einstein condensates, consisting of N1 interacting bosons of mass m1 driven by a force of amplitude fL,1 and N2 interacting bosons of mass m2 driven by a force of amplitude fL,2, is presented. The model generalizes the harmonic-interaction model for mixtures to the time-dependent domain. The resulting many-particle ground Floquet wavefunction and quasienergy, as well as the time-dependent densities and reduced density matrices, are prescribed explicitly and analyzed at the many-body and mean-field levels of theory for finite systems and at the limit of an infinite number of particles. We prove that the time-dependent densities per particle are given at the limit of an infinite number of particles by their respective mean-field quantities, and that the time-dependent reduced one-particle and two-particle density matrices per particle of the driven mixture are 100% condensed. Interestingly, the quasienergy per particle does not coincide with the mean-field value at this limit, unless the relative center-of-mass coordinate of the two Bose–Einstein condensates is not activated by the driving forces fL,1 and fL,2. As an application, we investigate the imprinting of angular momentum and its fluctuations when steering a Bose–Einstein condensate by an interacting bosonic impurity and the resulting modes of rotations. Whereas the expectation values per particle of the angular-momentum operator for the many-body and mean-field solutions coincide at the limit of an infinite number of particles, the respective fluctuations can differ substantially. The results are analyzed in terms of the transformation properties of the angular-momentum operator under translations and boosts, and as a function of the interactions between the particles. Implications are briefly discussed.

Exact solution of the non-Hermitian eigenvalue problem for electron orbital excitations in a hydrogen atom

A new way of solving the spectral problem for description of electronic excitations is demonstrated for a hydrogen atom. The applied methodology is based on the idea of the electronic excitations description without introducing boundary conditions to the eigenvalue problem for the square of the angular momentum operator. The eigenvalues of such an operator are considered as complex in general. As a result, the spectral problem for the Schrödinger equation becomes non-Hermitian with complex energy values. The imaginary part of the total energy helps to estimate the excitation lifetime within a unified scheme. The existence of the Stark shift of atomic energy levels and the collapse of the atomic spectra are confirmed.

Nonlinear extension of the u(3) algebra as the symmetry algebra of the three-dimensional anisotropic quantum harmonic oscillator with rational ratios of frequencies and the Nilsson model

The symmetry algebra of the N-dimensional anisotropic quantum har- monic oscillator with rational ratios of frequencies is constructed by a method of general applicability to quantum superintegrable systems. The special case of the 3-dim oscillator is studied in more detail, because of its relevance in the description of superdeformed nuclei and nuclear and atomic clusters. In this case the symmetry algebra turns out to be a nonlinear extension of the u(3) algebra. A generalized angular momentum operator useful for labeling the degenerate states is constructed, clarifying the connection of the present formalism to the Nilsson model.

Spherical HarmonicsYlm(θ,ϕ): Positive and Negative Integer Representations ofsu(1,1)forl-mandl+m

The azimuthal and magnetic quantum numbers of spherical harmonicsYlm(θ,ϕ)describe quantization corresponding to the magnitude andz-component of angular momentum operator in the framework of realization ofsu(2)Lie algebra symmetry. The azimuthal quantum numberlallocates to itself an additional ladder symmetry by the operators which are written in terms ofl. Here, it is shown that simultaneous realization of both symmetries inherits the positive and negative(l-m)- and(l+m)-integer discrete irreducible representations forsu(1,1)Lie algebra via the spherical harmonics on the sphere as a compact manifold. So, in addition to realizing the unitary irreducible representation ofsu(2)compact Lie algebra via theYlm(θ,ϕ)’s for a givenl, we can also representsu(1,1)noncompact Lie algebra by spherical harmonics for given values ofl-mandl+m.

A New Kind of Shift Operators for Infinite Circular and Spherical Wells

A new kind of shift operators for infinite circular and spherical wells is identified. These shift operators depend on all spatial variables of quantum systems and connect some eigenstates of confined systems of different radiiRsharing energy levels with a common eigenvalue. In circular well, the momentum operatorsP±=Px±iPyplay the role of shift operators. ThePxandPyoperators, the third projection of the orbital angular momentum operatorLz, and the HamiltonianHform a complete set of commuting operators with the SO(2) symmetry. In spherical well, the shift operators establish a novel relation betweenψlm(r)andψ(l±1)(m±1)(r).

DISAPPEARANCE OF SCHWINGER'S STRING AT THE CHARGE–MONOPOLE "MOLECULE"

An equivalence of total angular momentum operator of charge–monopole system to the momentum operator of a symmetrical quantum top is observed. This explicitly shows the string independence of Dirac's quantization condition leading to disappearance of Schwinger's string and reveals some properties of diatomic molecule for this system.