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The Chemical Educator

Localization and Spread of the Particle in a Box

J. J. C. Mulder

Published Mar 22, 2002• 0 citations
Publisher

Abstract

The most basic example of a quantum mechanical problem, the one-dimensional particle in a box, is revisited. Three aspects are treated. 1.It is shown that a number of textbooks give an incorrect result for the expectation value of x2, and, therefore, do not obtain the correct spread Δx. Consequently, the verification of the Heisenberg relation is also in error. 2. It is found that textbooks do not mention the origin dependence of expectation values, which is a nuisance, as the problem is evidently treated in the literature with two choices of origin. 3. Superposition of an infinite number of even (cosine) solutions of the one-dimensional particle in the box allows for an analytical demonstration of complete localization of the particle (Δx = 0).

DOI
10.1007/s00897020545a

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Classical mechanics traces a particle’s movement through space and time through x(t). For example, one may consider the case of a particle moving at constant speed (momentum p) in one direction or a particle bouncing back and forth at constant speed in a box. These problems are described in time and have direction and position associated with time etc. It is possible to define a probability P(x,t) in the classical picture based on delta time, the amount of time a particle spends in a little region of space dx. P(x,t), by itself, loses much relevant information present in the x(t) scenario because a particle moving to the right, or to the left, or bouncing back and forth all have the same probability, 1/L, where L is length. Furthermore, this probability is the same for all p (momentum) values. Thus a probability description, without extra information, is a subset of the relevant information in the problem. As a result, to describe the classical picture fully, one might say that a particle has a probability of 1/L, but also a mass mo and velocity +v (i.e. momentum mov nonrelativistically). For the particle bouncing back and forth in a box with constant p, one needs to give the initial position at time=0 and then a subsequent time (as well as the initial velocity and mo) in order to fully describe the problem, even though probability = 1/L. In the literature (see (1)), there have been many attempts to derive the quantum Schrodinger equation from a classical Fockker-Planck equation or a continuity equation (which follows from the Fokker-Planck equation as shown in (1)). The continuity equation contains a probability P(x,t) and a velocity(x,t) and is generally argued to represent classical physics. It does, if one retains appropriate classical conditions such as the discontinuity of density for a particle in a box (i.e. density=0 outside the box, but 1/L inside) and the notion of differing directions within the box. In fact, one may write density=W*(x,t)W(x,t) where W(x,t) is an ad hoc complex function and still retain compatibility with classical physics. If one does not, however, retain the classical conditions completely, nonclassical physics is introduced, even if density(x,t)=1/L. For example, in quantum mechanics density(x) is considered to be continuous in all x. Thus for a particle moving in a box, density outside the box is 0 so at the box wall it must also be 0. In the classical case, the density is 1 inside the box and 0 outside. There is a discontinuity classically and this cannot be changed and this contradicts the quantum mechanical picture. Thus quantum mechanics does not follow form classical Fokker-Planck or continuity equations which retain classical conditions.. Furthermore, because time is completely removed in the FP-continuity approach as applied to quantum mechanics, one cannot distinguish between forwards and backwards motion. As seen by the velocity field given in (1), v is zero for a bound particle which completely removes the sense of time and violates the classical physics conditions. It is, however, not zero for a particle moving in one direction. Thus there seems to be no issue in describing a Fokker-Planck-continuity equation as describing classical physics. One may even introduce density(x,t)= W*(x,t)W(x,t) provided one retains classical conditions allowing for discontinuity in density and different W(x,t) values at different times i.e. a discontinuity in W(x,t) at a box wall. If these conditions, however, are not met, then one no longer describes classical physics, but a new kind of physics (quantum physics). Thus one cannot argue that quantum mechanics follows from classical statistical Fokker-Planck-continuity equations. It may follow from these if one adds a set of extra conditions. Given these extra conditions, however, one could derive quantum mechanics without starting with classical density.

•Apr 24, 2023•0 citations
The most basic example of a quantum mechanical problem, the one-dimensional particle in a box, is revisited. Three aspects are treated. 1.It is shown that a number of textbooks give an incorrect result for the expectation value of x2, and, therefore, do not obtain the correct spread Δx. Consequently, the verification of the Heisenberg relation is also in error. 2. It is found that textbooks do not mention the origin dependence of expectation values, which is a nuisance, as the problem is evidently treated in the literature with two choices of origin. 3. Superposition of an infinite number of even (cosine) solutions of the one-dimensional particle in the box allows for an analytical demonstration of complete localization of the particle (Δx = 0).
Abstract Particle in a box is one of the applications of the Schrodinger equation. Schrodinger equation gives wave function which is used to determine the probability and expectation value of particle in a box. It is also can explain the energy levels of the particle. This study aimed to determine the probability, expectation values, and energy levels of a particle in a three-dimensional box with variations in main quantum numbers in each coordinate axis. The magnitude of the wave function and energy levels are influenced by the main quantum number and the width of the box. The results show that variations in the main quantum number influence the probability of particle in the three-dimensional box except for the width of the box <?CDATA L2\frac{L}{2}2L​?> L 2 and L the probability of particle showing the same value in all variations of the main quantum number. Variations in the main quantum number also influence the expectation value of particle in a three-dimensional box except for the width of the box L the expectation value shows the same value in all variations of the main quantum number. All variations of the main quantum number also influence the magnitude of the energy level of the particle.
In this paper we have solved analytically the Schrodinger equation for a microscopic particle in a one-dimensional box with two infinite walls, which the potential function inside it, has a linear form. Based on the solutions of this special quantum mechanical system, we have shown that as the quantum number approaches infinity the expectation values of microscopic particle position and square of the linear momentum are equal to the classical time average of particle position and its square of the linear momentum, respectively.
In a recent paper diffused in the literature, the quantum problem of a particle in a infinite square well potential was claimed to be solved via Laplace transform. Surprisingly, the correct solutions were found for an eigenvalue problem with variable defined on a finite range. As a matter of fact, the authors have misused the Laplace transform of the time-independent Schrödinger equation, and they have also used incorrectly the inversion process. In the present paper it is pointed out carefully and clearly those mistakes that might occur with the use of inappropriate methods for a given eigenvalue problem.
Abstract This paper revisits the textbook ‘particle in a box’, but from the point of view of Koopman–von Neumann (KvN) mechanics. KvN mechanics is a way to describe classical dynamics in a Hilbert space. That simple fact changes the usual expectation: hard walls do not force energy quantization here. We show, in a clear and physical way, why a KvN particle confined between two ideal walls still has a continuous range of energies. With the correct wall condition, one that captures ordinary elastic reflection rather than ‘vanishing at the boundary,’ the KvN description naturally produces spatial confinement without discrete energy levels. Beyond establishing this result, we also clarify a common root of confusion that can arise when one attempts to solve this problem: treating the KvN wavefunction as though it were a quantum probability amplitude in position space alone leads to the wrong boundary picture and, consequently, to the wrong conclusion about quantization.
A free particle is shown to possess any non-negative energy value. Its position is described by a localized wave function called a wave packet. The solution to the particle in infinite potential well problem displays how the concept of energy quantization appears in quantum mechanics. Like the particle in an infinite well, the particle in a finite well shows discretization of energy. But unlike the particle in an infinite well, the particle in a finite well exhibits a non-zero probability of being found outside the well leading to the concept of quantum-mechanical tunneling.
Classical mechanics traces a particle’s movement through space and time through x(t). For example, one may consider the case of a particle moving at constant speed (momentum p) in one direction or a particle bouncing back and forth at constant speed in a box. These problems are described in time and have direction and position associated with time etc. It is possible to define a probability P(x,t) in the classical picture based on delta time, the amount of time a particle spends in a little region of space dx. P(x,t), by itself, loses much relevant information present in the x(t) scenario because a particle moving to the right, or to the left, or bouncing back and forth all have the same probability, 1/L, where L is length. Furthermore, this probability is the same for all p (momentum) values. Thus a probability description, without extra information, is a subset of the relevant information in the problem. As a result, to describe the classical picture fully, one might say that a particle has a probability of 1/L, but also a mass mo and velocity +v (i.e. momentum mov nonrelativistically). For the particle bouncing back and forth in a box with constant p, one needs to give the initial position at time=0 and then a subsequent time (as well as the initial velocity and mo) in order to fully describe the problem, even though probability = 1/L. In the literature (see (1)), there have been many attempts to derive the quantum Schrodinger equation from a classical Fockker-Planck equation or a continuity equation (which follows from the Fokker-Planck equation as shown in (1)). The continuity equation contains a probability P(x,t) and a velocity(x,t) and is generally argued to represent classical physics. It does, if one retains appropriate classical conditions such as the discontinuity of density for a particle in a box (i.e. density=0 outside the box, but 1/L inside) and the notion of differing directions within the box. In fact, one may write density=W*(x,t)W(x,t) where W(x,t) is an ad hoc complex function and still retain compatibility with classical physics. If one does not, however, retain the classical conditions completely, nonclassical physics is introduced, even if density(x,t)=1/L. For example, in quantum mechanics density(x) is considered to be continuous in all x. Thus for a particle moving in a box, density outside the box is 0 so at the box wall it must also be 0. In the classical case, the density is 1 inside the box and 0 outside. There is a discontinuity classically and this cannot be changed and this contradicts the quantum mechanical picture. Thus quantum mechanics does not follow form classical Fokker-Planck or continuity equations which retain classical conditions.. Furthermore, because time is completely removed in the FP-continuity approach as applied to quantum mechanics, one cannot distinguish between forwards and backwards motion. As seen by the velocity field given in (1), v is zero for a bound particle which completely removes the sense of time and violates the classical physics conditions. It is, however, not zero for a particle moving in one direction. Thus there seems to be no issue in describing a Fokker-Planck-continuity equation as describing classical physics. One may even introduce density(x,t)= W*(x,t)W(x,t) provided one retains classical conditions allowing for discontinuity in density and different W(x,t) values at different times i.e. a discontinuity in W(x,t) at a box wall. If these conditions, however, are not met, then one no longer describes classical physics, but a new kind of physics (quantum physics). Thus one cannot argue that quantum mechanics follows from classical statistical Fokker-Planck-continuity equations. It may follow from these if one adds a set of extra conditions. Given these extra conditions, however, one could derive quantum mechanics without starting with classical density.