Harmonic oscillators in relativistic quantum mechanics

Relativistic generalisations of the harmonic oscillator are analysed. Lévy–Leblond, Dirac and Klein–Gordon equations which in the limit of a non-relativistic and spinless particle transform into Schrödinger equation for the harmonic oscillator are constructed. Properties of their solutions, in particular the structure of their spectra, are analysed. Applications to modelling phenomena relevant in quantum chemistry are briefly discussed.     

Algebraic approximation to the Franck–Condon factors for the Morse oscillator

An algebraic approach is proposed to calculate the Franck–Condon factors for the Morse potential of diatomic molecules. The Morse oscillator is approximated by means of a fourth-order anharmonic oscillator. In the second-quantized formalism, this anharmonic Hamiltonian is diagonalized by way of the Bogoliubov–Tyablikov transformation. The Franck–Condon factors are estimated using the harmonic frequency equivalent and the recurrence relations for the Franck–Condon factors of the harmonic oscillator. Overlap integrals are shown for three band systems and compared with values calculated with an RKR potential. Excellent agreement is achieved.     

The Scaled Hermite–Weber Basis Still Highly Competitive

The effectiveness of the usual harmonic oscillator basis is demonstrated on a wide class of Schrödinger Hamiltonians with various spectral properties. More specifically, it is shown numerically that an appropriately scaled Hermite–Weber basis yields extremely accurate results not only for the energy eigenvalues which differ slighly from the harmonic oscillator levels, but also for the states which reflect a purely anharmonic character.     

On the time‐dependent solutions of the Schrödinger's equation. II. The one‐mode field perturbed harmonic oscillator

The solution of the time‐dependent Schrödinger's equation for a perturbed harmonic oscillator is obtained using a solvable Lie algebra. We choose a harmonic oscillator interacting with a one‐mode field, where the perturbation happens to be periodic in time. This leads to one of the simplest Floquet problems. Using the Wei–Norman theorem, the Floquet wave function is obtained as well as the semiclassical Floquet shift in the energy. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Harmonic oscillator tensors. IV. A tensorial approach to internal rotations in molecules

A mapping of 2×2 matrices into the space of single boson operators is shown to lead to the angular momentum operators that give rise to irreducible tensors for the harmonic oscillator. The mapping may also be used to define an axis of quantization. A rotation about this axis induces a wave function and Hamiltonian that may be applied to the study of internal rotations in molecules. The example of a molecule containing two coaxial symmetric tops is presented as a case in point. The case of a potential with a high barrier leads to the approximation of an internal rotation as a torsional oscillator and, consequently, to torsional oscillator tensors whose properties are the same as those of the harmonic oscillator. The possibility of studying more complex potentials is discussed. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 65 : 305–315, 1997     

The Coulomb Green's function in IR3 and its relation to the harmonic oscillator in IR4

A very simple derivation of the Coulomb Green's function in IR³ is presented, which is based on an application of the Kustaanheimo–Stiefel transformation directly to the equation defining the harmonic oscillator Green's function in IR⁴. The representation that we obtain makes it possible to Fourier transform the Green's function with respect to its space variables by means of a simple Gaussian integration. The method that we use can readily be applied to several other Hamiltonians.     

Simultaneous integration of mixed quantum-classical systems by density matrix evolution equations using interaction representation and adaptive time step integrator

A density matrix evolution method [H. J. C. Berendsen and J. Mavri, J. Phys. Chem., 97, 13464 (1993)] to simulate the dynamics of quantum systems embedded in a classical environment is applied to study the inelastic collisions of a classical particle with a five-level quantum harmonic oscillator. We improved the numerical performance by rewriting the Liouville–von Neumann equation in the interaction representation and so eliminated the frequencies of the unperturbed oscillator. Furthermore, replacement of the fixed time step fourth-order Runge–Kutta integrator with an adaptive step size control fourth-order Runge–Kutta resulted in significantly lower computational effort at the same desired accuracy. © 1996 by John Wiley & Sons, Inc.     

Theory of multidimensional wavepacket propagation

Ehrenfest's theorem implies that a gaussian remains a gaussian when propagated in a general (time-dependent and multidimensional) harmonic potential. We shall prove that the statement remains true with the replacement of a gaussian with a harmonic oscillator. For the one-dimensional case, this is implicit in the work of Meyer. Here, we prove it more generally for the multidimensional case. A complete, orthonormal, evolving basis of harmonic oscillator wavefunctions can then be constructed by using a local, time-dependent, harmonic approximation to the potential. An evolving wavepacket in the actual potential can be expanded in the basis set, and the coefficients of the expansion obey a set of coupled, linear, first-order differential equations. The theory has practical applications for processes such as Raman scattering, photodissociation, and other time-dependent processes that can benefit from multidimensional wavepacket propagation.     

A simplified model for the predissociation of diatomic molecules

A model consisting of a harmonic oscillator well and a repulsive inverse square potential, coupled by a delta function, is solved. We find the S-function for this case and study its poles as a function of the coupling strength. These poles show how the harmonic levels shift and broaden as the two potential curves couple and predissociation occurs. A “new state” is found when the energy threshold is just below the first excited state of the harmonic oscillator.     

Minimum uncertainty wavelets in non-relativistic super-symmetric quantum mechanics

We consider the connection to the harmonic oscillator, super-symmetric quantum mechanics (SUSY-QM) and coherent states of the recently derived constrained Heisenberg “minimum uncertainty” (μ-) wavelets [Phys Rev Lett 85:5263 (2000); Phys Rev A65: 052106-1 (2002); J Phys Chem A107:7318 (2003)]. We analyze several new types of raising and lowering operators,which also can be viewed as arising from a (non-unitary) similarity transformation of the Harmonic Oscillator Hamiltonian and ladder operators. We show that these new ladder operators lead to a new SUSY formalism for harmonic oscillation, so that the μ-wavelets naturally manifest SUSY properties. Using these new ladder operators, we construct coherent and supercoherent states for the oscillator. In the discussion, we consider possible implications of similarity transformations for quantum mechanics. In an appendix we consider the classical limit of the μ-wavelet oscillator.     

Variational method for calculating the anharmonic vibrations of polyatomic molecules using a combined morse-anharmonic basis taking into account the fragmentary structure of molecules

A method of variational solution of anharmonic vibration problems using a mixed Morse—anharmonic basis is proposed. The basis functions are the products of the Morse oscillator eigenfunctions for vibrations of peripheral bonds, the harmonic oscillator eigenfunctions for almost harmonic skeletal and deformation vibrations, and the anharmonic basis functions for essentially anharmonic skeletal and deformation vibrations. The anharmonic basis wave functions are taken as a linear combination of the Morse and harmonic oscillator eigenfunctions. The introduction of the combined Morse—anharmonic functions allows one to factorize the solution of a problem into a series of individual blocks according to the fragmentary structure of molecules. Volgograd Pedagogical University. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 2, pp. 231–238, March–April, 1995. Translated by I. Izvekova     

Harmonic oscillator tensors in contact transformation theory

The application of contact transformation theory to the perturbed harmonic oscillator is reexamined in the light of the harmonic oscillator tensors previously presented. It is found that the recasting of the formalism of this problem in terms of harmonic oscillator tensors results in great simplifications, most of which stem from the introduction of the additional algebraic quantum numbers (l, m). The order of magnitude of each fragment of the Hamiltonian is easily recognizable, and the diagonal and nondiagonal parts contained therein are readily identifiable. The determination of the contact transformation operator is reduced to a simple formula. First, an analysis is made for a single mode of vibration, and it is subsequently extended to a multimode case. The perturbed diatomic vibrator is presented as an example.     

Perturbational and variational treatments of the Morse oscillator

The Morse oscillator hamiltonian is expressed as an infinite expansion in powers of a natural perturbation parameter, the square root of the anharmonicity constant, relative to the simple harmonic oscillator as zeroth-order hamiltonian. A transformation of variables leads to a hamiltonian which involves terms no higher than second order in this natural perturbation parameter. In both cases, the exact bound state eigenvalues of the Morse oscillator are given by second-order perturbation theory. The Schrödinger equation corresponding to the transformed Morse hamiltonian is solved variationally, via a complete set expansion in simple harmonic oscillator eigenstates. Accurate approximations to the exact eigenvalues and eigenfunctions of bound states of the Morse oscillator can be obtained for all but the very highest levels.     

Harmonic oscillator tensors. II. angular momentum expressions of matrix elements of vibrational operators

The spatial symmetries of the harmonic oscillator and the recently found irreducible tensors constructed from the associated annihilation and creation operators are exploited to obtain new expressions for the elements of the matrix representatives of several examples of vibrational operators. Since all vibrational operators are expressible in terms of the irreducible tensors, their matrix elements reflect the angular momentum symmetry inherent in them, for the results derived here are in terms of the Clebsch–Gordan coefficients and the isoscalar factors that arise from the couplinig rule of the irreducible tensors. Familiarity with the mathematical properties of these quantities derived from the elementary theory of angular momentum facilitates the evaluation of many vibrational operators that may be of importance in the study of potentials in this basis. In particular, it is shown that the nonvanishing of matrix elements is governed by a law of conservation of angular momentum along the axis of quantization of the nondegenerate harmonic oscillator. © 1993 John Wiley & Sons, Inc.     

A uniform semiclassical representation of transition probabilities derived from factorization formulas

Factorization formulas are used to derive a uniform semiclassical approximation of transition probabilities. The latter are determined in the analytical form where the basis transition probabilities are set by the analytical formula. As an example, we consider the rigid rotor, harmonic oscillator, and Morse oscillator in collisions with structureless particles.     

Converged vibrational energy levels and quantum mechanical vibrational partition function of ethane

The vibrational partition function of ethane is calculated in the temperature range of 200-600 K using well-converged energy levels that were calculated by vibrational configuration interaction, and the results are compared to the harmonic oscillator partition function. This provides the first test of the harmonic oscillator approximation for a molecule with more than five atoms. The absolute free energies computed by the harmonic oscillator approximation are in error by 0.59-0.62 kcal/mol over the 200-600 K temperature range.     

On the decay of highly excited oscillator in a crystal

The diagonal density matrix elements are found for a dynamical subsystem which is either anharmonic or harmonic highly excited oscillator interacting with the crystal vibrations. For the extreme case of the infinitely highly excited oscillator the result is exact. Different limiting cases are considered. In particular for the harmonic oscillator the validity criterion for the balance equation is found.     

A general expression for matrix elements of reciprocal powers of the displacement coordinateq in the harmonic oscillator basis

A formula is derived that allows one to determine the matrix elements of an arbitrary integral reciprocal power of the dimensionless displacement coordinate q of the harmonic oscillator from those ofq ^–1 in an exact manner. This relation is obtained from the use of the chain rule and irreducible tensors expressed in terms of the creation and annihilation operators of the harmonic oscillator.     

Analytic quantum mechanics of the morse oscillator

The approximate eigenfunctions of the Morse oscillator, expressed in terms of Laguerre polynomials, are shown to form an approximately orthogonal basis. Analytic expressions for the matrix elements of common operators are obtained within this representation. With such matrix elements in closed form, the Morse oscillator becomes, as the harmonic oscillator has been, a practical building block in molecular theory.