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The Journal of Chemical Physics

Quantum mechanical streamlines. IV. Collision of two spheres with square potential wells or barriers

Joseph O. Hirschfelder, Kwong Tin Tang

Published Jul 1, 1976• 71 citations
Publisher

Abstract

Quantum mechanical streamlines and probability density contours help in the understanding of collision dynamics by showing what happens during the collision. This is illustrated by considering the elastic scattering of two particles which interact with a spherically symmetric square potential, V (r) =0 when r≳a and V (r) =C when r<a, where the constant C is negative for a potential well and positive for a barrier. The streamlines and density contours completely determine the wavefunction (which is separable in r and ϑ and independent of φ) since the pre-exponential factor is the square root of the density and the phase is everywhere perpendicular to the streamlines. The streamlines often form quantized vortices surrounding wavefunction nodes. Since the nodal regions are circular rings, the vortices are toroidal (like smoke rings). If one or both of the particles is charged, the vortex ring corresponds to a collisional magnetic moment. The distortion of the streamlines provides a visual explanation of the large collision cross sections. In S-wave resonances 4πr2=σ0, where r is the distance from the origin to the center of the outermost vortex and σ0 is the cross section of the S-wave component. Thus, r is essentially the ’’scattering length.’’ In P-wave resonances (where again r is the radial distance to the outermost vortex), 1.85πr2?σ1 and in D-wave resonances, 1.45πr2?σ2. In the square well resonances, the density inside of the interaction sphere has the shape of the dominant wave and often has maxima hundreds to thousands of times greater than the density of the incident wave. By happenstance, whenever the potential well has the proper depth to form a newly bound D state, there is a Ramsauer–Townsend effect so that (for small energy of the incident wave) the total scattering cross section is very small;outside the interaction zone, the streamlines are only slightly deflected by the potential well;inside, the streamlines are deflected towards the symmetry axis and the probability density is concentrated near this axis

DOI
10.1063/1.432790

Related papers

Quantum mechanical streamlines. I. Square potential barrier

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Exact numerical calculations are made for the scattering of quantum mechanical particles from a square two-dimensional potential barrier. This treatment is an exact analog of both frustrated total reflection of perpendicularly polarized light and the longitudinal Goos-Hänchen shift. Quantum mechanical streamlines (which are analogous to either classical mechanical trajectories or optical rays) are plotted. These streamlines are smooth, continuous, and have continuous first derivatives even through the classically forbidden region. The streamlines form quantized vortices surrounding each of the nodal points (which result from interference between the incident and reflected waves). Similar vortices occur in reactive collisions of H + H2 (McCullough and Wyatt; Kuppermann, Adams, and Truhlar) and undoubtedly play an important role in molecular collision dynamics. The theory for these vortices is given in a companion paper. A comparison is given between our numerical calculations and the stationary phase approximation (SPA). Although our incident wave packet has a half-width of more than one de Broglie wavelength in contrast to the SPA which replaces the diffuse beams by rays with delta function profiles, the agreement was surprisingly good for both the Goos-Hänchen shifts and for the reflection coefficients. However, we found that the Goos-Hänchen shift for the transmitted beam is significantly smaller than for the reflected beam, although in the stationary phase approximation these two shifts are equal. Furthermore, we found that the scattering from the potential barrier has very little effect on the shape of the wave packets. The power series expansion of the incident Debye-Picht wave packet ψI has an extremely small radius of convergence, whereas the power series for ψI*ψI has a radius of convergence of more than two de Broglie wavelengths. The imaginary velocity viis introduced into the Madelung-Landau-London hydrodynamical formulation of quantum mechanics. The corresponding imaginary streamlines will be considered in a forthcoming paper. The time-independent Schrödinger equation for real wavefunctions is reduced to solving the nonlinear first order partial differential equation: ℏ▿·vi = 2(E − V) + vi2. Here, vi is irrotational. This equation may lead to interesting new methods of solving the Schrödinger equation. It does lead to a generalization of the Prager-Hirschfelder perturbation scheme which invokes an electrostatic analogy. The philosophical implications of the hydrodynamical formulation of quantum mechanics are discussed. Penetration of a one-dimensional square potential barrier is used to demonstrate exactly how tunneling occurs by particles ``riding over the barrier'' à la Bohm. Cases are cited where quantum and classical mechanical motions are identical.

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Abstract It is well-known that the problem of the collision between two particles interacting according to the inverse square law is exactly soluble on the wave mechanics, and that the solution yields the same scattering laws as the classical theory. If, however, the two particles are identical, e.g., two electrons or two α-particles, this is not necessarily the case; for the wave functions used must be antisymmetrical or symmetrical in the co-ordinates of the two particles; and this may affect the scattering laws. In this paper we shall discuss the collision between two particles possessing spin, such as electrons, and also between two particles without spin, such as α-particles. Assuming an inverse square law force between the particles, and neglecting the actual spin forces, we shall deduce from the symmetry properties of the wave functions a scatter­ing law differing considerably from the classical. We shall also mention the various methods by which the effect could be observed, and give some experi­mental evidence in its favour. The application of the exclusion principle to collision problems has been discussed by the author in a previous paper. Suppose we wish to describe the motion of two particles interacting in any field of force. We obtain a solution w(r1 r2) of the wave equation, where r1 refers to the position of the first particle, and r2 to that of the second. If we did not use antisymmetrical wave functions, we should argue that the probability that the first particle should be at r1 and the second at r 2 would be |w (r1 r2)|2, and therefore the probability that one particle should be at r1 and the other at r2 would be |w (r1 r2)|2 + |w(r2 r1)|

Proceedings of the Royal Society of London Series A Containing Papers of a Mathematical and Physical Character•Jan 1, 1930•222 citations
Quantum mechanical streamlines and probability density contours help in the understanding of collision dynamics by showing what happens during the collision. This is illustrated by considering the elastic scattering of two particles which interact with a spherically symmetric square potential, V (r) =0 when r≳a and V (r) =C when r<a, where the constant C is negative for a potential well and positive for a barrier. The streamlines and density contours completely determine the wavefunction (which is separable in r and ϑ and independent of φ) since the pre-exponential factor is the square root of the density and the phase is everywhere perpendicular to the streamlines. The streamlines often form quantized vortices surrounding wavefunction nodes. Since the nodal regions are circular rings, the vortices are toroidal (like smoke rings). If one or both of the particles is charged, the vortex ring corresponds to a collisional magnetic moment. The distortion of the streamlines provides a visual explanation of the large collision cross sections. In S-wave resonances 4πr2=σ0, where r is the distance from the origin to the center of the outermost vortex and σ0 is the cross section of the S-wave component. Thus, r is essentially the ’’scattering length.’’ In P-wave resonances (where again r is the radial distance to the outermost vortex), 1.85πr2?σ1 and in D-wave resonances, 1.45πr2?σ2. In the square well resonances, the density inside of the interaction sphere has the shape of the dominant wave and often has maxima hundreds to thousands of times greater than the density of the incident wave. By happenstance, whenever the potential well has the proper depth to form a newly bound D state, there is a Ramsauer–Townsend effect so that (for small energy of the incident wave) the total scattering cross section is very small;outside the interaction zone, the streamlines are only slightly deflected by the potential well;inside, the streamlines are deflected towards the symmetry axis and the probability density is concentrated near this axis
Exact numerical calculations are made for the scattering of quantum mechanical particles from a square two-dimensional potential barrier. This treatment is an exact analog of both frustrated total reflection of perpendicularly polarized light and the longitudinal Goos-Hänchen shift. Quantum mechanical streamlines (which are analogous to either classical mechanical trajectories or optical rays) are plotted. These streamlines are smooth, continuous, and have continuous first derivatives even through the classically forbidden region. The streamlines form quantized vortices surrounding each of the nodal points (which result from interference between the incident and reflected waves). Similar vortices occur in reactive collisions of H + H2 (McCullough and Wyatt; Kuppermann, Adams, and Truhlar) and undoubtedly play an important role in molecular collision dynamics. The theory for these vortices is given in a companion paper. A comparison is given between our numerical calculations and the stationary phase approximation (SPA). Although our incident wave packet has a half-width of more than one de Broglie wavelength in contrast to the SPA which replaces the diffuse beams by rays with delta function profiles, the agreement was surprisingly good for both the Goos-Hänchen shifts and for the reflection coefficients. However, we found that the Goos-Hänchen shift for the transmitted beam is significantly smaller than for the reflected beam, although in the stationary phase approximation these two shifts are equal. Furthermore, we found that the scattering from the potential barrier has very little effect on the shape of the wave packets. The power series expansion of the incident Debye-Picht wave packet ψI has an extremely small radius of convergence, whereas the power series for ψI*ψI has a radius of convergence of more than two de Broglie wavelengths. The imaginary velocity viis introduced into the Madelung-Landau-London hydrodynamical formulation of quantum mechanics. The corresponding imaginary streamlines will be considered in a forthcoming paper. The time-independent Schrödinger equation for real wavefunctions is reduced to solving the nonlinear first order partial differential equation: ℏ▿·vi = 2(E − V) + vi2. Here, vi is irrotational. This equation may lead to interesting new methods of solving the Schrödinger equation. It does lead to a generalization of the Prager-Hirschfelder perturbation scheme which invokes an electrostatic analogy. The philosophical implications of the hydrodynamical formulation of quantum mechanics are discussed. Penetration of a one-dimensional square potential barrier is used to demonstrate exactly how tunneling occurs by particles ``riding over the barrier'' à la Bohm. Cases are cited where quantum and classical mechanical motions are identical.
An atom–diatomic molecule collision is simulated by considering an idealized potential energy surface which is a two-dimensional duct with an adjustable potential in the corner region. This potential is symmetric with respect to an interchange of the x and y Cartesian coordinates. Explicit expressions for the wavefunctions are obtained which make use of this symmetry. Also analytical relations are obtained between the transmission and reflection coefficients and their phases. Quantum mechanical streamlines are computer graphed for a large number of energies and positive, negative, and zero values of the potential energy in the corner region. Special attention is given to the quantized vortices (surrounding wavefunction nodes) which appear in the streamlines. When only one energy channel is open, the streamlines are symmetric and the flux is antisymmetric. This occurs because the wavefunction is a linear combination (with complex coefficients) of two real solutions, one symmetric, the other antisymmetric. When two energy channels are open, the streamlines are no longer symmetric. This is because the two wavefunctions are now linear combinations (with complex coefficients) of four real solutions. Although the second wavefunction is expressed in terms of the first, their streamlines have quite different patterns. From the Argand diagrams, it is clear that the reflection, transmission, and Feshbach-type resonances which occur correspond to the Breit–Wigner type. At a reflection resonance energy all of the streamlines disappear; at slightly higher energy, the streamlines reappear with the same vortices as before but rotating in the opposite direction. The probability density is only symmetric at transmission resonance energies. At energies higher than the Feshbach-type resonance energy (where a second energy channel becomes open), the streamlines pattern ceases to be symmetric and the flux antisymmetric. The exact quantum mechanical wavefunction for this idealized model is the same as the exact semiclassical wavefunction. These wavefunctions are infinite series. It is found that for the low energies which we consider, an excellent approximation is obtained by truncating the series after the first two terms. This corresponds to a semiclassical wavefunction formed from two manifolds of classical trajectories.
The flux of probability density corresponding to a complex wavefunction, ψ=ψr+iψi, can form vortices which rotate about a nodal region of ψ, and have integer values of the circulation numbers. For one particle wavefunctions (or for approximate natural spin molecular orbitals), the vortices are either axial or toroidal. The axial vortices have angular momentum dipole moments which are usually quantized only if the wave function is an eigenfunction of Lz. The axial vortices interact with homogeneous magnetic fields whereas the toroidal interact with inhomogeneous magnetic fields. Toroidal vortices are easily created or annihilated by a perturbation which moves the nodal surface of ψi relative to the nodal surface of ψr so that these surfaces intersect or become separated. Thus, toroidal vortices are unstable and may be important only near resonance. However, axial vortices are stable since their creation requires (a) photon absorption or emission, (b) a perturbation (such as a magnetic field) which converts a real into a complex wavefunction, or (c) conversion of a toroidal into an axial vortex by expanding the nodal loop until a part of it reaches the boundary of configuration space. Thus, axial vortices should play an important role in energy transfer, photochemical processes, etc., and their circulation numbers should be good quantum numbers. A method for determining generalized first-order density matrices and natural spin–orbitals for use in scattering problems is proposed.
Abstract Having examined free particles and particles that are confined in space by a potential energy term, we now consider the impact of a disturbance in the flat energy landscape for a free particle. By disturbance we means some kind of fixed “obstacle” which is either a positive (repelling) or negative (attractive) potential. We are interested in determining the impact on the free particle. Continuing to work mostly in one dimension, the particle described by a plane wave corresponding to momentum moving in the positive direction (a positive k−vector in the x−direction), we study elastic scattering. In one dimension, this means that we determine the probability that the particle is transmitted (continuing in the forward direction) or reflected (now moving in the backward direction.) We will also determine the nature of the solution inside the potential and in the case that the potential energy maximum is greater than the kinetic energy of the particle, we will show that the particle tunnels through the barrier. Interestingly, when we have two barriers, we can find conditions where the probability that the particle is transmitted is unity. This is the result of resonance, a feature of the wave-like nature of the particle’s wave function.
Abstract It is well-known that the problem of the collision between two particles interacting according to the inverse square law is exactly soluble on the wave mechanics, and that the solution yields the same scattering laws as the classical theory. If, however, the two particles are identical, e.g., two electrons or two α-particles, this is not necessarily the case; for the wave functions used must be antisymmetrical or symmetrical in the co-ordinates of the two particles; and this may affect the scattering laws. In this paper we shall discuss the collision between two particles possessing spin, such as electrons, and also between two particles without spin, such as α-particles. Assuming an inverse square law force between the particles, and neglecting the actual spin forces, we shall deduce from the symmetry properties of the wave functions a scatter­ing law differing considerably from the classical. We shall also mention the various methods by which the effect could be observed, and give some experi­mental evidence in its favour. The application of the exclusion principle to collision problems has been discussed by the author in a previous paper. Suppose we wish to describe the motion of two particles interacting in any field of force. We obtain a solution w(r1 r2) of the wave equation, where r1 refers to the position of the first particle, and r2 to that of the second. If we did not use antisymmetrical wave functions, we should argue that the probability that the first particle should be at r1 and the second at r 2 would be |w (r1 r2)|2, and therefore the probability that one particle should be at r1 and the other at r2 would be |w (r1 r2)|2 + |w(r2 r1)|