In quantum mechanics, an energy level is degenerate if it corresponds to two or more different measurable states of a quantum system. Conversely, two or more different states of a quantum mechanical system are said to be degenerate if they give the same value of energy upon measurement. The number of different states corresponding to a particular energy level is known as the degree of degeneracy (or simply the degeneracy) of the level. It is represented mathematically by the Hamiltonian for the system having more than one linearly independent eigenstate with the same energy eigenvalue.[1] When this is the case, energy alone is not enough to characterize what state the system is in, and other quantum numbers are needed to characterize the exact state when distinction is desired. In classical mechanics, this can be understood in terms of different possible trajectories corresponding to the same energy.
Degeneracy plays a fundamental role in quantum statistical mechanics. For an -particle system in three dimensions, a single energy level may correspond to several different wave functions or energy states. These degenerate states at the same level all have an equal probability of being filled. The number of such states gives the degeneracy of a particular energy level.
The possible states of a quantum mechanical system may be treated mathematically as abstract vectors in a separable, complex Hilbert space, while the observables may be represented by linear Hermitian operators acting upon them. By selecting a suitable basis, the components of these vectors and the matrix elements of the operators in that basis may be determined. If is a matrix, a non-zero vector, and is a scalar, such that
AX=λX
AX1=λX1
AX2=λX2
X1
X2
The eigenvalues of the matrices representing physical observables in quantum mechanics give the measurable values of these observables while the eigenstates corresponding to these eigenvalues give the possible states in which the system may be found, upon measurement. The measurable values of the energy of a quantum system are given by the eigenvalues of the Hamiltonian operator, while its eigenstates give the possible energy states of the system. A value of energy is said to be degenerate if there exist at least two linearly independent energy states associated with it. Moreover, any linear combination of two or more degenerate eigenstates is also an eigenstate of the Hamiltonian operator corresponding to the same energy eigenvalue. This clearly follows from the fact that the eigenspace of the energy value eigenvalue is a subspace (being the kernel of the Hamiltonian minus times the identity), hence is closed under linear combinations.
In the absence of degeneracy, if a measured value of energy of a quantum system is determined, the corresponding state of the system is assumed to be known, since only one eigenstate corresponds to each energy eigenvalue. However, if the Hamiltonian
\hat{H}
En
En
|En,i\rangle
In this case, the probability that the energy value measured for a system in the state
|\psi\rangle
En
This section intends to illustrate the existence of degenerate energy levels in quantum systems studied in different dimensions. The study of one and two-dimensional systems aids the conceptual understanding of more complex systems.
|\psi\rangle
V(x)
E
V
E
M,x0
M ≠ 0
\forallx>x0
V(x)-E\geqM2
V
Two-dimensional quantum systems exist in all three states of matter and much of the variety seen in three dimensional matter can be created in two dimensions. Real two-dimensional materials are made of monoatomic layers on the surface of solids. Some examples of two-dimensional electron systems achieved experimentally include MOSFET, two-dimensional superlattices of Helium, Neon, Argon, Xenon etc. and surface of liquid Helium. The presence of degenerate energy levels is studied in the cases of Particle in a box and two-dimensional harmonic oscillator, which act as useful mathematical models for several real world systems.
Consider a free particle in a plane of dimensions
Lx
Ly
|\psi\rangle
nx,ny=1,2,3,...
nx
ny
For some commensurate ratios of the two lengths
Lx
Ly
Lx/Ly=p/q
(nx,ny)
(pny/q,qnx/p)
In this case, the dimensions of the box
Lx=Ly=L
Since
nx
ny
nx
ny
E=50
\pi2\hbar2 | |
2mL2 |
Degrees of degeneracy of different energy levels for a particle in a square box:
nx | ny | E\left(
\right) | Degeneracy | |||
---|---|---|---|---|---|---|
1 | 1 | 2 | 1 | |||
2 1 | 1 2 | 5 5 | 2 | |||
2 | 2 | 8 | 1 | |||
3 1 | 1 3 | 10 10 | 2 | |||
3 2 | 2 3 | 13 13 | 2 | |||
4 1 | 1 4 | 17 17 | 2 | |||
3 | 3 | 18 | 1 | |||
... | ... | ... | ... | |||
7 5 1 | 1 5 7 | 50 50 50 | 3 | |||
... | ... | ... | ... | |||
8 7 4 1 | 1 4 7 8 | 65 65 65 65 | 4 | |||
... | ... | ... | ... | |||
9 7 6 2 | 2 6 7 9 | 85 85 85 85 | 4 | |||
... | ... | ... | ... | |||
11 10 5 2 | 2 5 10 11 | 125 125 125 125 | 4 | |||
... | ... | ... | ... | |||
14 10 2 | 2 10 14 | 200 200 200 | 3 | |||
... | ... | ... | ... | |||
17 13 7 | 7 13 17 | 338 338 338 | 3 | |||
In this case, the dimensions of the box
Lx=Ly=Lz=L
Since
nx
ny
nz
If two operators
\hat{A}
\hat{B}
[\hat{A},\hat{B}]=0
|\psi\rangle
\hat{A}
\hat{B}|\psi\rang
\hat{A}
λ
\hat{B}|\psi\rangle
Eλ
\hat{A}
\hat{B}
For two commuting observables and, one can construct an orthonormal basis of the state space with eigenvectors common to the two operators. However,
λ
\hat{A}
\hat{A}
\hat{B}
\hat{B}
\hat{A}
\hat{A}
\hat{B}
\hat{A}
\hat{A}
\hat{B}
If a given observable A is non-degenerate, there exists a unique basis formed by its eigenvectors. On the other hand, if one or several eigenvalues of
\hat{A}
\hat{B}
\hat{A}
\hat{A}
\hat{B}
\hat{A}
\hat{B}
\hat{C}
\hat{A}
\hat{B}
It follows that the eigenfunctions of the Hamiltonian of a quantum system with a common energy value must be labelled by giving some additional information, which can be done by choosing an operator that commutes with the Hamiltonian. These additional labels required naming of a unique energy eigenfunction and are usually related to the constants of motion of the system.
The parity operator is defined by its action in the
|r\rangle
\pm1
Now, an even operator
\hat{A}
\hat{B}
\hat{p}2
\hat{H}
\hat{H}
P|\psi\rangle
\hat{H}
|\psi\rangle
The physical origin of degeneracy in a quantum-mechanical system is often the presence of some symmetry in the system. Studying the symmetry of a quantum system can, in some cases, enable us to find the energy levels and degeneracies without solving the Schrödinger equation, hence reducing effort.
Mathematically, the relation of degeneracy with symmetry can be clarified as follows. Consider a symmetry operation associated with a unitary operator . Under such an operation, the new Hamiltonian is related to the original Hamiltonian by a similarity transformation generated by the operator, such that
H'=SHS-1=SHS\dagger
|\alpha\rangle
S|\alpha\rangle
|\alpha\rangle
S|\alpha\rangle
\epsilon
S(\epsilon)|\alpha\rangle
The set of all operators which commute with the Hamiltonian of a quantum system are said to form the symmetry group of the Hamiltonian. The commutators of the generators of this group determine the algebra of the group. An n-dimensional representation of the Symmetry group preserves the multiplication table of the symmetry operators. The possible degeneracies of the Hamiltonian with a particular symmetry group are given by the dimensionalities of the irreducible representations of the group. The eigenfunctions corresponding to a n-fold degenerate eigenvalue form a basis for a n-dimensional irreducible representation of the Symmetry group of the Hamiltonian.
Degeneracies in a quantum system can be systematic or accidental in nature.
This is also called a geometrical or normal degeneracy and arises due to the presence of some kind of symmetry in the system under consideration, i.e. the invariance of the Hamiltonian under a certain operation, as described above. The representation obtained from a normal degeneracy is irreducible and the corresponding eigenfunctions form a basis for this representation.
It is a type of degeneracy resulting from some special features of the system or the functional form of the potential under consideration, and is related possibly to a hidden dynamical symmetry in the system.[3] It also results in conserved quantities, which are often not easy to identify. Accidental symmetries lead to these additional degeneracies in the discrete energy spectrum. An accidental degeneracy can be due to the fact that the group of the Hamiltonian is not complete. These degeneracies are connected to the existence of bound orbits in classical Physics.
For a particle in a central potential, the Laplace–Runge–Lenz vector is a conserved quantity resulting from an accidental degeneracy, in addition to the conservation of angular momentum due to rotational invariance.
For a particle moving on a cone under the influence of and potentials, centred at the tip of the cone, the conserved quantities corresponding to accidental symmetry will be two components of an equivalent of the Runge-Lenz vector, in addition to one component of the angular momentum vector. These quantities generate SU(2) symmetry for both potentials.
A particle moving under the influence of a constant magnetic field, undergoing cyclotron motion on a circular orbit is another important example of an accidental symmetry. The symmetry multiplets in this case are the Landau levels which are infinitely degenerate.
See main article: Hydrogen Atom.
\hat{L}2
\hat{L}z
\hat{S}2
\hat{S}z
\ell
m\ell
s
ms
The energy levels in the hydrogen atom depend only on the principal quantum number . For a given, all the states corresponding to
\ell=0,\ldots,n-1
(2\ell+1)
m\ell=-\ell,\ldots,\ell
The degeneracy with respect to
m\ell
\ell
It is a spinless particle of mass m moving in three-dimensional space, subject to a central force whose absolute value is proportional to the distance of the particle from the centre of force. It is said to be isotropic since the potential
V(r)
\omega
Since the state space of such a particle is the tensor product of the state spaces associated with the individual one-dimensional wave functions, the time-independent Schrödinger equation for such a system is given by-
So, the energy eigenvalues are or, where n is a non-negative integer.So, the energy levels are degenerate and the degree of degeneracy is equal to the number of different sets
\{nx,ny,nz\}
n
n
nx
ny
nz
nx
n+1
ny
nz
nx
n
ny
nz
n-nx+1
n
n
n=0
1
The degeneracy in a quantum mechanical system may be removed if the underlying symmetry is broken by an external perturbation. This causes splitting in the degenerate energy levels. This is essentially a splitting of the original irreducible representations into lower-dimensional such representations of the perturbed system.
Mathematically, the splitting due to the application of a small perturbation potential can be calculated using time-independent degenerate perturbation theory. This is an approximation scheme that can be applied to find the solution to the eigenvalue equation for the Hamiltonian H of a quantum system with an applied perturbation, given the solution for the Hamiltonian H0 for the unperturbed system. It involves expanding the eigenvalues and eigenkets of the Hamiltonian H in a perturbation series. The degenerate eigenstates with a given energy eigenvalue form a vector subspace, but not every basis of eigenstates of this space is a good starting point for perturbation theory, because typically there would not be any eigenstates of the perturbed system near them. The correct basis to choose is one that diagonalizes the perturbation Hamiltonian within the degenerate subspace.
Some important examples of physical situations where degenerate energy levels of a quantum system are split by the application of an external perturbation are given below.
A two-level system essentially refers to a physical system having two states whose energies are close together and very different from those of the other states of the system. All calculations for such a system are performed on a two-dimensional subspace of the state space.
If the ground state of a physical system is two-fold degenerate, any coupling between the two corresponding states lowers the energy of the ground state of the system, and makes it more stable.
If
E1
E2
E1=E2=E
W
Examples of two-state systems in which the degeneracy in energy states is broken by the presence of off-diagonal terms in the Hamiltonian resulting from an internal interaction due to an inherent property of the system include:
See main article: Fine structure.
The corrections to the Coulomb interaction between the electron and the proton in a Hydrogen atom due to relativistic motion and spin–orbit coupling result in breaking the degeneracy in energy levels for different values of l corresponding to a single principal quantum number n.
The perturbation Hamiltonian due to relativistic correction is given bywhere
p
m
|nlm\rangle
Now
p4=4m2(H0+e2/r)2
\alpha
The spin–orbit interaction refers to the interaction between the intrinsic magnetic moment of the electron with the magnetic field experienced by it due to the relative motion with the proton. The interaction Hamiltonian iswhich may be written as
The first order energy correction in the
|j,m,\ell,1/2\rangle
a0
See main article: Zeeman effect.
\vec{m}
Taking into consideration the orbital and spin angular momenta,
L
S
m\ell=-eL/2m
ms=-eS/m
\muB={e\hbar}/2m
mj
In case of the strong-field Zeeman effect, when the applied field is strong enough, so that the orbital and spin angular momenta decouple, the good quantum numbers are now n, l, ml, and ms. Here, Lz and Sz are conserved, so the perturbation Hamiltonian is given by-assuming the magnetic field to be along the z-direction. So,For each value of m, there are two possible values of ms,
\pm1/2
See main article: Stark effect.
The splitting of the energy levels of an atom or molecule when subjected to an external electric field is known as the Stark effect.
For the hydrogen atom, the perturbation Hamiltonian isif the electric field is chosen along the z-direction.
The energy corrections due to the applied field are given by the expectation value of
\hat{H}s
|n\ellm\rangle
\langlen\ellm\ell|z|n1\ell1m\ell1\rangle\ne0
\ell=\ell1\pm1
m\ell=m\ell1
The degeneracy is lifted only for certain states obeying the selection rules, in the first order. The first-order splitting in the energy levels for the degenerate states
|2,0,0\rangle
|2,1,0\rangle
\Delta
E | |
2,1,m\ell |
=\pm|e|\hbar2/(mee2)E