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CRC Press eBooks

Generalization to Three Dimensions

Walter Wilcox

Published Aug 23, 2019• 0 citations
Publisher

Abstract

Synopsis: Direct product spaces are encountered in the generalization to higher dimensions, and the connection to wave function separability is discussed. The spherical coordinate basis is introduced in preparation for discussing spherically symmetric potentials. Angular momentum operators and properties are examined, and a complete set of compatible observables is determined. The angular momentum eigenvalues and eigenstates are determined using ladder operators, and the connection to spherical harmonics is made. The stage is set for understanding the Schrödinger radial equation.

DOI
10.1201/b22285-6

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Generalization to Three Dimensions

Walter Wilcox

Synopsis: Direct product spaces are encountered in the generalization to higher dimensions, and the connection to wave function separability is discussed. ƒe spherical coordinate basis is introduced in preparation for discussing spherically symmetric potentials. Angular momentum operators and properties are examined, and a complete set of compatible observables is determined. ƒe angular momentum eigenvalues and eigenstates are determined using ladder operators and the connection to spherical harmonics is made. ƒe stage is set for understanding the Schrödinger radial equation.

CRC Press eBooks•Apr 19, 2016•0 citations

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Abstract In this chapter, we go to three dimensions in space and look at the solution of the time independent Schrödinger equation for the hydrogen atom. The Hamiltonian is then the kinetic energy plus the potential energy due to the Coulomb coupling between the positively charged nucleus and the electron. We construct the angular momentum operator and find that the partial differential equation for the angular momentum eigenfunctions of the spherical coordinates θ,ϕ is the same as the angular part of the ∇2 operator in spherical coordinates. The angular momentum eigenfunctions are the spherical harmonics, with two quantum numbers, l and m, and the solution to the radial part of the Hamiltonian including the Coulomb potential are Laguerre polynomials with one quantum number, called the principle quantum number, n. The hydrogen wave function is the product of a Laguerre polynomial and a spherical harmonic with three quantum numbers. Since these are two- and three-dimensional functions for angular momentum and hydrogen respectively, they are best understood in a series of plots. The chapter concludes by giving the historical letter names to specific orbitals, since they continue to be used today.

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Angular momentum theory provides a mathematical foundation for the rotation of the eigenvectors of the angular momentum operator, the spherical harmonics functions. A useful property of spherical harmonics is that their rotation in 3D space corresponds to rotation in the virtual space of their azimuthal degrees of freedom. In addition to that, spherical harmonics functions that have different orbital indices do not mix. Given that spherical harmonics functions have known rotation properties, and that any arbitrary function can be expanded in a series of spherical harmonics, this property allows the rotation of an electrostatic potential when it is expanded in the series of spherical harmonics. In this chapter, the exponential form of the rotation operator, the rotation matrix for a 3D rotation of the coordinate system, and the principles of rotation of vectors and functions are described. The chapter provides a detailed self-contained introduction to the theory of angular momentum, derives the commutative properties of the angular momentum operator, and explains shift operators, while minimizing references to quantum mechanics and entirely avoiding group theory.

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The usual explicit expressions for spherical harmonics are derived by a method which does not involve the solution of differential equations or the use of angular momentum operators in spherical polar form. Instead a raising operator constructed from an arbitrary vector is used together with the usual angular momentum raising and lowering operators. The method is first presented as simply as possible in Schrödinger representation using position as the vector. Then it is generalized to an arbitrary vector and arbitrary integral angular momentum without using a particular representation. Finally it is shown how a conserved vector (other than angular momentum) of a central system can be used to reveal properties of the energy eigenstates. As an example, eigenstates of the hydrogen atom are found using the Runge-Lenz vector.

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Introductory Quantum Mechanics

Rodney C. Greenhow

Part 1: the need for the quantum mechanics quantization of radiation the special theory of relativity wave-particle duality the nature of matter waves the uncertainty principle the Bohr atom. Part 2 Schrodinger's equation: the postulates of quantum mechanics the wave equation the wave equation in three dimensions the time-independent Schrodinger equation stationary states normalisation probability flux physical constraints on the wave-function wave packets Gaussian wave-packets and the uncertainty principle. Part 3 One-dimensional potential wells: potential wells the one-dimensional infinite square well discussion of infinite square-well results eigenvalue equations the finite square well finite square well eigenfunctions the control of the wave-function by the wave equation numerical integration of Schrodinger's equation continuum solutions of the square-well potential interpretation of unbound-particle wave functions the double potential well the quantum bouncer electric fields and the tilted well the harmonic oscillator - introduction the quantum oscillator discussion of harmonic oscillator eigenvalues and eigenfunctions the classical probability density more potential wells. Part 4 Schrodinger's equation in three dimensions: particle in a three dimensional box degeneracy Schrodingers equation in spherical polar coordinates - the hydrogen atom normalisation. Part 5 Formal development of quantum mechanics: eigenvalues equations, operators and measurements the momentum operator, eigenvalues and eigenfunctions the position operator and its eigenfunctions Hermitian operators orthogonality of eigenfunctions the expansion postulate example - the b-decay of tritium expectation values compatibility of observables - commutators non-commuting operators time-dependence of expectation values - Ehrenfest's theorem abstract operators - the parity operator, matrix mechanics. Part 6 Angular momentum: angular momentum operators angular momentum commutators angular momentum eigenvalues and eigenfunctions interpretation of angular momentum eigenvalues interpretation of angular momentum eigenfunctions the Stern-Gerlach apparatus and electron spin spin operators - the Pauli Spin matrices the Zeeman effect measurements in quantum mechanics. Part 7 Spherically symmetric potential wells: the rigid rotator the radial equation the hydrogen atom and hydrogen like ions the isotropic harmonic oscillator molecular vibrations - the Morse potential the spherical square well general properties of spherically symmetric potential wells. (Part contents)

•Jan 1, 1990•15 citations
Synopsis: Direct product spaces are encountered in the generalization to higher dimensions, and the connection to wave function separability is discussed. The spherical coordinate basis is introduced in preparation for discussing spherically symmetric potentials. Angular momentum operators and properties are examined, and a complete set of compatible observables is determined. The angular momentum eigenvalues and eigenstates are determined using ladder operators, and the connection to spherical harmonics is made. The stage is set for understanding the Schrödinger radial equation.
Synopsis: Direct product spaces are encountered in the generalization to higher dimensions, and the connection to wave function separability is discussed. ƒe spherical coordinate basis is introduced in preparation for discussing spherically symmetric potentials. Angular momentum operators and properties are examined, and a complete set of compatible observables is determined. ƒe angular momentum eigenvalues and eigenstates are determined using ladder operators and the connection to spherical harmonics is made. ƒe stage is set for understanding the Schrödinger radial equation.
Abstract In this chapter, we go to three dimensions in space and look at the solution of the time independent Schrödinger equation for the hydrogen atom. The Hamiltonian is then the kinetic energy plus the potential energy due to the Coulomb coupling between the positively charged nucleus and the electron. We construct the angular momentum operator and find that the partial differential equation for the angular momentum eigenfunctions of the spherical coordinates θ,ϕ is the same as the angular part of the ∇2 operator in spherical coordinates. The angular momentum eigenfunctions are the spherical harmonics, with two quantum numbers, l and m, and the solution to the radial part of the Hamiltonian including the Coulomb potential are Laguerre polynomials with one quantum number, called the principle quantum number, n. The hydrogen wave function is the product of a Laguerre polynomial and a spherical harmonic with three quantum numbers. Since these are two- and three-dimensional functions for angular momentum and hydrogen respectively, they are best understood in a series of plots. The chapter concludes by giving the historical letter names to specific orbitals, since they continue to be used today.
Angular momentum theory provides a mathematical foundation for the rotation of the eigenvectors of the angular momentum operator, the spherical harmonics functions. A useful property of spherical harmonics is that their rotation in 3D space corresponds to rotation in the virtual space of their azimuthal degrees of freedom. In addition to that, spherical harmonics functions that have different orbital indices do not mix. Given that spherical harmonics functions have known rotation properties, and that any arbitrary function can be expanded in a series of spherical harmonics, this property allows the rotation of an electrostatic potential when it is expanded in the series of spherical harmonics. In this chapter, the exponential form of the rotation operator, the rotation matrix for a 3D rotation of the coordinate system, and the principles of rotation of vectors and functions are described. The chapter provides a detailed self-contained introduction to the theory of angular momentum, derives the commutative properties of the angular momentum operator, and explains shift operators, while minimizing references to quantum mechanics and entirely avoiding group theory.
The usual explicit expressions for spherical harmonics are derived by a method which does not involve the solution of differential equations or the use of angular momentum operators in spherical polar form. Instead a raising operator constructed from an arbitrary vector is used together with the usual angular momentum raising and lowering operators. The method is first presented as simply as possible in Schrödinger representation using position as the vector. Then it is generalized to an arbitrary vector and arbitrary integral angular momentum without using a particular representation. Finally it is shown how a conserved vector (other than angular momentum) of a central system can be used to reveal properties of the energy eigenstates. As an example, eigenstates of the hydrogen atom are found using the Runge-Lenz vector.
The quantization of orbital angular momentum can be introduced simply through the model of the two- and three-dimensional simple harmonic oscillator. Most of the analysis is carried out in the familiar Cartesian coordinate system in which the simple harmonic oscillator Schrödinger equation is separable. Angular momentum eigenfunctions are constructed by superposition, and the resulting functions easily transformed into spherical coordinates. The angle-dependent parts of the solutions are the spherical harmonics, which are the orbital angular momentum eigenfunctions for all central potentials including the Coulomb potential of the hydrogen atom. The method also introduces the separation of variables technique and provides practice in applying the concepts of completeness, orthogonality, superposition of states, and alternative representations.
Part 1: the need for the quantum mechanics quantization of radiation the special theory of relativity wave-particle duality the nature of matter waves the uncertainty principle the Bohr atom. Part 2 Schrodinger's equation: the postulates of quantum mechanics the wave equation the wave equation in three dimensions the time-independent Schrodinger equation stationary states normalisation probability flux physical constraints on the wave-function wave packets Gaussian wave-packets and the uncertainty principle. Part 3 One-dimensional potential wells: potential wells the one-dimensional infinite square well discussion of infinite square-well results eigenvalue equations the finite square well finite square well eigenfunctions the control of the wave-function by the wave equation numerical integration of Schrodinger's equation continuum solutions of the square-well potential interpretation of unbound-particle wave functions the double potential well the quantum bouncer electric fields and the tilted well the harmonic oscillator - introduction the quantum oscillator discussion of harmonic oscillator eigenvalues and eigenfunctions the classical probability density more potential wells. Part 4 Schrodinger's equation in three dimensions: particle in a three dimensional box degeneracy Schrodingers equation in spherical polar coordinates - the hydrogen atom normalisation. Part 5 Formal development of quantum mechanics: eigenvalues equations, operators and measurements the momentum operator, eigenvalues and eigenfunctions the position operator and its eigenfunctions Hermitian operators orthogonality of eigenfunctions the expansion postulate example - the b-decay of tritium expectation values compatibility of observables - commutators non-commuting operators time-dependence of expectation values - Ehrenfest's theorem abstract operators - the parity operator, matrix mechanics. Part 6 Angular momentum: angular momentum operators angular momentum commutators angular momentum eigenvalues and eigenfunctions interpretation of angular momentum eigenvalues interpretation of angular momentum eigenfunctions the Stern-Gerlach apparatus and electron spin spin operators - the Pauli Spin matrices the Zeeman effect measurements in quantum mechanics. Part 7 Spherically symmetric potential wells: the rigid rotator the radial equation the hydrogen atom and hydrogen like ions the isotropic harmonic oscillator molecular vibrations - the Morse potential the spherical square well general properties of spherically symmetric potential wells. (Part contents)