quantum mechanics and spectroscopy: by substituting the classical momentum with the momentum operator, quantized energy levels (or stationary states) were obtained. This quantization is a direct consequence of the boundary conditions, which required wavefunctions to be zero at the edge of the box. Since the energy depends on this quantum number n, one usually writes Eq. (2.32) as
(2.33)
Substituting these energy eigenvalues back into Eq. (2.27)
(2.27)
one obtains
which are the wave functions for the PiB.
2.3.3 Normalization and Orthogonality of the PiB Wavefunctions
In Eq. (2.34), “A” is an amplitude factor still undefined at this point. To determine “A,” one argues as follows: since the square of the wavefunction is defined as the probability of finding the particle, the square of the wavefunction written in Eq. (2.34), integrated over the length of the box, must be unity, since the particle is known to be in the box. This leads to the normalization condition
(2.35)
Using the integral relationship
the amplitude A is obtained as follows:
Thus, the normalized stationary‐state wavefunctions for the particle in a box can be written in a final form as
(2.38)
The stationary‐state (time‐independent) wavefunctions and energies are depicted in Figure 2.2, panel (a). Although one refers to these wavefunctions as time‐independent, they may be considered as standing waves in which the amplitudes oscillate between the extremes as shown in Figure 2.3 and resemble the motion of a plugged string. Time independency then refers to the fact that the system will stay in one of these standing wave patterns forever or until perturbed by electromagnetic radiation.
The probability of finding the particle at any given position x is shown in Figure 2.2, panel (b). These traces are the squares of the wavefunctions and depict that for higher levels of n, the probability of finding the particle moves away from the center to the periphery of the box.
The PiB wavefunctions form an orthonormal vector space, which implies that
δmn in Eq. (2.39) is referred to as the Kronecker symbol that has the value of 1 if n = m and is zero otherwise. The wavefunctions' normality was established above by normalizing them (Eqs. (2.36) and (2.37)); in order to demonstrate that they are orthogonal, the integral
Figure 2.3 (a) Representation of the particle‐in‐a‐box wavefunctions shown in Figure 2.2 as standing waves. (b) Visualization of the orthogonality of the first two PiB wavefunctions. See text for detail.
needs to