In quantum mechanics, the particle in a box model (also known as the infinite potential well or the infinite square well)
describes a particle free to move in a small space surrounded by
impenetrable barriers. The model is mainly used as a hypothetical
example to illustrate the differences between classical
and quantum systems. In classical systems, for example, a ball trapped
inside a large box, the particle can move at any speed within the box
and it is no more likely to be found at one position than another.
However, when the well becomes very narrow (on the scale of a few
nanometres), quantum effects become important. The particle may only
occupy certain positive energy levels. Likewise, it can never have zero energy, meaning that the particle can
never "sit still". Additionally, it is more likely to be found at
certain positions than at others, depending on its energy level. The
particle may never be detected at certain positions, known as spatial
nodes.
The particle in a box model is one of the very few problems in
quantum mechanics which can be solved analytically, without
approximations. Due to its simplicity, the model allows insight into
quantum effects without the need for complicated mathematics. It serves
as a simple illustration of how energy quantization
(energy levels), which are found in more complicated quantum systems
such as atoms and molecules, come about. It is one of the first quantum
mechanics problems taught in undergraduate physics courses, and it is
commonly used as an approximation for more complicated quantum systems.
One-dimensional solution
The
barriers outside a one-dimensional box have infinitely large potential,
while the interior of the box has a constant, zero potential.
The simplest form of the particle in a box model considers a
one-dimensional system. Here, the particle may only move backwards and
forwards along a straight line with impenetrable barriers at either end.
The walls of a one-dimensional box may be visualised as regions of space with an infinitely large potential energy. Conversely, the interior of the box has a constant, zero potential energy.
This means that no forces act upon the particle inside the box and it
can move freely in that region. However, infinitely large forces
repel the particle if it touches the walls of the box, preventing it
from escaping. The potential energy in this model is given as
where L is the length of the box, xc is the location of the center of the box and x is the position of the particle within the box. Simple cases include the centered box (xc = 0 ) and the shifted box (xc = L/2 ).
Position wave function
In quantum mechanics, the wavefunction
gives the most fundamental description of the behavior of a particle;
the measurable properties of the particle (such as its position,
momentum and energy) may all be derived from the wavefunction.
The wavefunction can be found by solving the Schrödinger equation for the system
Inside the box, no forces act upon the particle, which means that
the part of the wavefunction inside the box oscillates through space
and time with the same form as a free particle:
Inside the box, no forces act upon the particle, which means that the
part of the wavefunction inside the box oscillates through space and
time with the same form as a free particle:
(1)
where and are arbitrary complex numbers. The frequency of the oscillations through space and time is given by the wavenumber and the angular frequency respectively. These are both related to the total energy of the particle by the expression
which is known as the dispersion relation for a free particle. Here one must notice that now, since the particle is not entirely free but under the influence of a potential (the potential V described above), the energy of the particle given above is not the same thing as where p is the momentum of the particle, and thus the wavenumber k
above actually describes the energy states of the particle, not the
momentum states (i.e. it turns out that the momentum of the particle is
not given by ). In this sense, it is quite dangerous to call the number k a wavenumber, since it is not related to momentum like "wavenumber" usually is. The rationale for calling k
the wavenumber is that it enumerates the number of crests that the
wavefunction has inside the box, and in this sense it is a wavenumber.
This discrepancy can be seen more clearly below, when we find out that
the energy spectrum of the particle is discrete (only discrete values of
energy are allowed) but the momentum spectrum is continuous (momentum
can vary continuously) and in particular, the relation
for the energy and momentum of the particle does not hold. As said
above, the reason this relation between energy and momentum does not
hold is that the particle is not free, but there is a potential V in the system, and the energy of the particle is , where T is the kinetic and V the potential energy.
Initial wavefunctions for the first four states in a one-dimensional particle in a box
The size (or amplitude) of the wavefunction at a given position is related to the probability of finding a particle there by . The wavefunction must therefore vanish everywhere beyond the edges of the box. Also, the amplitude of the wavefunction may not "jump" abruptly from one point to the next. These two conditions are only satisfied by wavefunctions with the form
where
,
and
,
where n is a positive integer (1,2,3,4...). For a shifted box (xc = L/2), the solution is particularly simple. The simplest solutions, or both yield the trivial wavefunction , which describes a particle that does not exist anywhere in the system. Negative values of are neglected, since they give wavefunctions identical to the positive solutions except for a physically unimportant sign change. Here one sees that only a discrete set of energy values and wavenumbers k
are allowed for the particle. Usually in quantum mechanics it is also
demanded that the derivative of the wavefunction in addition to the
wavefunction itself be continuous; here this demand would lead to the
only solution being the constant zero function, which is not what we
desire, so we give up this demand (as this system with infinite
potential can be regarded as a nonphysical abstract limiting case, we
can treat it as such and "bend the rules"). Note that giving up this
demand means that the wavefunction is not a differentiable function at
the boundary of the box, and thus it can be said that the wavefunction
does not solve the Schrödinger equation at the boundary points and (but does solve everywhere else).
Finally, the unknown constant may be found by normalizing the wavefunction so that the total probability density of finding the particle in the system is 1. It follows that
Thus, A may be any complex number with absolute value√2/L; these different values of A yield the same physical state, so A = √2/L can be selected to simplify.
It is expected that the eigenvalues, i.e., the energy of the box should be the same regardless of its position in space, but changes. Notice that
represents a phase shift in the wave function, This phase shift has no
effect when solving the Schrödinger equation, and therefore does not
affect the eigenvalue.
Momentum wave function
The momentum wavefunction is proportional to the Fourier transform of the position wavefunction. With (note that the parameter k describing the momentum wavefunction below is not exactly the special kn above, linked to the energy eigenvalues), the momentum wavefunction is given by
where sinc is the cardinal sine sinc function, sinc(x)=sin(x)/x. For the centered box (xc= 0),
the solution is real and particularly simple, since the phase factor on
the right reduces to unity. (With care, it can be written as an even
function of p.)
It can be seen that the momentum spectrum in this wave packet is
continuous, and one may conclude that for the energy state described by
the wavenumber kn, the momentum can, when measured, also attain other values beyond .
Hence, it also appears that, since the energy is for the nth eigenstate, the relation does not strictly hold for the measured momentum p; the energy eigenstate
is not a momentum eigenstate, and, in fact, not even a superposition of
two momentum eigenstates, as one might be tempted to imagine from
equation (1) above: peculiarly, it has no well-defined momentum before measurement!
Position and momentum probability distributions
In
classical physics, the particle can be detected anywhere in the box
with equal probability. In quantum mechanics, however, the probability
density for finding a particle at a given position is derived from the
wavefunction as
For the particle in a box, the probability density for finding the
particle at a given position depends upon its state, and is given by
Thus, for any value of n greater than one, there are regions within the box for which , indicating that spatial nodes exist at which the particle cannot be found.
In quantum mechanics, the average, or expectation value of the position of a particle is given by
For the steady state particle in a box, it can be shown that the average position is always ,
regardless of the state of the particle. For a superposition of
states, the expectation value of the position will change based on the
cross term which is proportional to .
The variance in the position is a measure of the uncertainty in position of the particle:
The probability density for finding a particle with a given momentum is derived from the wavefunction as . As with position, the probability density for finding the particle at a given momentum depends upon its state, and is given by
where, again, . The expectation value for the momentum is then calculated to be zero, and the variance in the momentum is calculated to be:
The uncertainties in position and momentum ( and ) are defined as being equal to the square root of their respective variances, so that:
This product increases with increasing n, having a minimum value for n=1. The value of this product for n=1 is about equal to 0.568 which obeys the Heisenberg uncertainty principle, which states that the product will be greater than or equal to .
Another measure of uncertainty in position is the information entropy of the probability distribution Hx:
where x0 is an arbitrary reference length.
Another measure of uncertainty in momentum is the information entropy of the probability distribution Hp:
where p0 is an arbitrary reference momentum. The integral is difficult to express analytically for general n, but in the limit as n approaches infinity:
For , the sum of the position and momentum entropies yields:
which satisfies the quantum entropic uncertainty principle.
Energy levels
The
energy of a particle in a box (black circles) and a free particle (grey
line) both depend upon wavenumber in the same way. However, the
particle in a box may only have certain, discrete energy levels.
The energies which correspond with each of the permitted wavenumbers may be written as
.
The energy levels increase with ,
meaning that high energy levels are separated from each other by a
greater amount than low energy levels are. The lowest possible energy
for the particle (its zero-point energy) is found in state 1, which is given by
The particle, therefore, always has a positive energy. This
contrasts with classical systems, where the particle can have zero
energy by resting motionlessly. This can be explained in terms of the uncertainty principle, which states that the product of the uncertainties in the position and momentum of a particle is limited by
It can be shown that the uncertainty in the position of the particle is proportional to the width of the box. Thus, the uncertainty in momentum is roughly inversely proportional to the width of the box.[9] The kinetic energy of a particle is given by ,
and hence the minimum kinetic energy of the particle in a box is
inversely proportional to the mass and the square of the well width, in
qualitative agreement with the calculation above.
Higher-dimensional boxes
(Hyper)rectangular walls
The wavefunction of a 2D well with nx=4 and ny=4
If a particle is trapped in a two-dimensional box, it may freely move in the and -directions, between barriers separated by lengths and respectively. For a centered box, the position wave function may be written including the length of the box as .
Using a similar approach to that of the one-dimensional box, it can be
shown that the wavefunctions and energies for a centered box are given
respectively by
where the three-dimensional wavevector is given by:
.
In general for an n-dimensional box, the solutions are
The 1-dimensional momentum wave functions may likewise be represented by and the momentum wave function for an n-dimensional centered box is then:
An interesting feature of the above solutions is that when two or more of the lengths are the same (e.g. ), there are multiple wavefunctions corresponding to the same total energy. For example, the wavefunction with has the same energy as the wavefunction with . This situation is called degeneracy and for the case where exactly two degenerate wavefunctions have the same energy that energy level is said to be doubly degenerate.
Degeneracy results from symmetry in the system. For the above case
two of the lengths are equal so the system is symmetric with respect to a
90° rotation.
More complicated wall shapes
The wavefunction for a quantum-mechanical particle in a box whose walls have arbitrary shape is given by the Helmholtz equation subject to the boundary condition that the wavefunction vanishes at the walls. These systems are studied in the field of quantum chaos for wall shapes whose corresponding dynamical billiard tables are non-integrable.
Applications
Because
of its mathematical simplicity, the particle in a box model is used to
find approximate solutions for more complex physical systems in which a
particle is trapped in a narrow region of low electric potential between two high potential barriers. These quantum well systems are particularly important in optoelectronics, and are used in devices such as the quantum well laser, the quantum well infrared photodetector and the quantum-confined Stark effect
modulator. It is also used to model a lattice in the Kronig-Penny model
and for a finite metal with the free electron approximation.
Conjugated polyenes
β-carotene is a conjugated polyene
Conjugated polyene systems can be modeled using particle in a box.
The conjugated system of electrons can be modeled as a one dimensional
box with length equal to the total bond distance from one terminus of
the polyene to the other. In this case each pair of electrons in each π
bond corresponds to one energy level. The energy difference between two
energy levels, nf and ni is:
The difference between the ground state energy, n, and the first
excited state, n+1, corresponds to the energy required to excite the
system. This energy has a specific wavelength, and therefore color of
light, related by:
A common example of this phenomenon is in β-carotene. β-carotene (C40H56)
is a conjugated polyene with an orange color and a molecular length of
approximately 3.8 nm (though its chain length is only approximately
2.4 nm). Due to β-carotene's high level of conjugation,
electrons are dispersed throughout the length of the molecule, allowing
one to model it as a one-dimensional particle in a box. β-carotene has
11 carbon-carbon double bonds in conjugation;
each of those double bonds contains two π-electrons, therefore
β-carotene has 22 π-electrons. With two electrons per energy level,
β-carotene can be treated as a particle in a box at energy level n=11. Therefore, the minimum energy needed to excite an electron to the next energy level can be calculated, n=12, as follows (recalling that the mass of an electron is 9.109 × 10−31 kg):
This indicates that β-carotene primarily absorbs light in the
infrared spectrum, therefore it would appear white to a human eye.
However the observed wavelength is 450 nm, indicating that the particle in a box is not a perfect model for this system.
Quantum well laser
The particle in a box model can be applied to quantum well lasers,
which are laser diodes consisting of one semiconductor “well” material
sandwiched between two other semiconductor layers of different material .
Because the layers of this sandwich are very thin (the middle layer is
typically about 100 Å thick), quantum confinement effects can be observed.
The idea that quantum effects could be harnessed to create better laser
diodes originated in the 1970s. The quantum well laser was patented in
1976 by R. Dingle and C. H. Henry.
Specifically, the quantum well’s behavior can be represented by
the particle in a finite well model. Two boundary conditions must be
selected. The first is that the wave function must be continuous. Often,
the second boundary condition is chosen to be the derivative of the
wave function must be continuous across the boundary, but in the case of
the quantum well the masses are different on either side of the
boundary. Instead, the second boundary condition is chosen to conserve
particle flux as,
which is consistent with experiment. The solution to the finite well
particle in a box must be solved numerically, resulting in wave
functions that are sine functions inside the quantum well and
exponentially decaying functions in the barriers.
This quantization of the energy levels of the electrons allows a
quantum well laser to emit light more efficiently than conventional
semiconductor lasers.
Due to their small size, quantum dots do not showcase the bulk
properties of the specified semi-conductor but rather show quantised
energy states.
This effect is known as the quantum confinement and has led to numerous
applications of quantum dots such as the quantum well laser.
Researchers at Princeton University have recently built a quantum well laser which is no bigger than a grain of rice.
The laser is powered by a single electron which passes through two
quantum dots; a double quantum dot. The electron moves from a state of
higher energy, to a state of lower energy whilst emitting photons in the
microwave region. These photons bounce off mirrors to create a beam of
light; the laser.
The quantum well laser is heavily based on the interaction
between light and electrons. This relationship is a key component in
quantum mechanical theories which include the De Broglie Wavelength and
Particle in a box. The double quantum dot allows scientists to gain full
control over the movement of an electron which consequently results in
the production of a laser beam.
Quantum dots
Quantum dots are extremely small semiconductors (on the scale of nanometers). They display quantum confinement in that the electrons cannot escape the “dot”, thus allowing particle-in-a-box approximations to be applied. Their behavior can be described by three-dimensional particle-in-a-box energy quantization equations.
The energy gap of a quantum dot is the energy gap between its valence and conduction bands. This energy gap is equal to the band gap of the bulk material plus the energy equation derived from particle-in-a-box, which gives the energy for electrons and holes. This can be seen in the following equation, where and are the effective masses of the electron and hole, is radius of the dot, and is Planck's constant:
Hence, the energy gap of the quantum dot is inversely
proportional to the square of the “length of the box,” i.e. the radius
of the quantum dot.
Manipulation of the band gap allows for the absorption and
emission of specific wavelengths of light, as energy is inversely
proportional to wavelength. The smaller the quantum dot, the larger the band gap and thus the shorter the wavelength absorbed.
Different semiconducting materials are used to synthesize quantum
dots of different sizes and therefore emit different wavelengths of
light.
Materials that normally emit light in the visible region are often used
and their sizes are fine-tuned so that certain colors are emitted. Typical substances used to synthesize quantum dots are cadmium (Cd) and selenium (Se). For example, when the electrons of two nanometer CdSe quantum dots relax after excitation, blue light is emitted. Similarly, red light is emitted in four nanometer CdSe quantum dots.
Quantum dots have a variety of functions including but not limited to fluorescent dyes, transistors, LEDs, solar cells, and medical imaging via optical probes.
One function of quantum dots is their use in lymph node mapping,
which is feasible due to their unique ability to emit light in the near
infrared (NIR) region. Lymph node mapping allows surgeons to track if
and where cancerous cells exist.
Quantum dots are useful for these functions due to their emission
of brighter light, excitation by a wide variety of wavelengths, and
higher resistance to light than other substances.