Hamiltonian (quantum mechanics)
Encyclopedia
In quantum mechanics
, the Hamiltonian H, also or Ĥ, is the operator
corresponding to the total energy
of the system. Its spectrum is the set of possible outcomes when one measures the total energy of a system. Because of its close relation to the time-evolution of a system, it is of fundamental importance in most formulations of quantum theory.
, the Hamiltonian is commonly expressed as the sum of operators corresponding to the kinetic
and potential
energies of a system, in the form
(although this is not the technical definition of the Hamiltonian in classical mechanics
, it is the form it most commonly takes). The potential operator V typically takes the form of a function V(r,t) of position and time
, which simply acts on states as a multiplicative factor. The operator T corresponding to kinetic energy is constructed by analogy with the classical formula
with
the momentum and 
the mass.
Schrödinger
constructed his momentum operator
using the substitution
where
(Nabla
) is the gradient
operator, i is the unit imaginary number
, and
is the reduced Planck constant. Combining this with the potential term yields
which allows one to apply the Hamiltonian to systems described by a wave function
.
This is the approach commonly taken in introductory treatments of quantum mechanics, using the formalism of Schrödinger's wave mechanics. However, in the more general formalism
of Dirac
, the Hamiltonian is typically implemented as an operator on a Hilbert space
in the following way:
(From a mathematically rigorous point of view, care must be taken with the above assumptions. Operators on infinite-dimensional Hilbert spaces need not have eigenvalues (the set of eigenvalues does not necessarily coincide with the spectrum of an operator). However, all routine quantum mechanical calculations can be done using the physical formulation.)
evolution of quantum states. If
is the state of the system at time t, then
This equation is known as the Schrödinger equation
. (It takes the same form as the Hamilton–Jacobi equation
, which is one of the reasons H is also called the Hamiltonian.) Given the state at some initial time (t = 0), we can integrate it to obtain the state at any subsequent time. In particular, if H is independent of time, then
The exponential
operator on the right hand side of the Schrödinger equation is usually defined by the corresponding power series in H. One might notice that taking polynomials or power series of unbounded operator
s that are not defined everywhere may not make mathematical sense. Rigorously, to take functions of unbounded operators, a functional calculus
is required. In the case of the exponential function, the continuous
, or just the holomorphic functional calculus
suffices. We note again, however, that for common calculations the physicists' formulation is quite sufficient.
By the *-homomorphism
property of the functional calculus, the operator
is a unitary operator
. It is the time evolution
operator, or propagator, of a closed quantum system. If the Hamiltonian is time-independent, {U(t)} form a one parameter unitary group
(more than a semigroup); this gives rise to the physical principle of detailed balance
.
. A wave propagating in the x direction is a different state from one propagating in the y direction, but if they have the same wavelength, then their energies will be the same. When this happens, the states are said to be degenerate.
It turns out that degeneracy occurs whenever a nontrivial unitary operator U commutes with the Hamiltonian. To see this, suppose that
is an energy eigenket. Then 
is an energy eigenket with the same eigenvalue, since
Since U is nontrivial, at least one pair of
and 
must represent distinct states. Therefore, H has at least one pair of degenerate energy eigenkets. In the case of the free particle, the unitary operator which produces the symmetry is the rotation operator, which rotates the wavefunctions by some angle while otherwise preserving their shape.
The existence of a symmetry operator implies the existence of a conserved
observable. Let G be the Hermitian generator of U:
It is straightforward to show that if U commutes with H, then so does G:
Therefore,
In obtaining this result, we have used the Schrödinger equation, as well as its dual
,
Thus, the expected value
of the observable G is conserved for any state of the system. In the case of the free particle, the conserved quantity is the angular momentum
.
's equations in classical Hamiltonian mechanics
have a direct analogy in quantum mechanics. Suppose we have a set of basis states
, which need not necessarily be eigenstates of the energy. For simplicity, we assume that they are discrete, and that they are orthonormal, i.e.,
Note that these basis states are assumed to be independent of time. We will assume that the Hamiltonian is also independent of time.
The instantaneous state of the system at time t,
, can be expanded in terms of these basis states:
where
The coefficients an(t) are complex
variables. We can treat them as coordinates which specify the state of the system, like the position and momentum coordinates which specify a classical system. Like classical coordinates, they are generally not constant in time, and their time dependence gives rise to the time dependence of the system as a whole.
The expectation value of the Hamiltonian of this state, which is also the mean energy, is
where the last step was obtained by expanding
in terms of the basis states.
Each of the an(t)s actually corresponds to two independent degrees of freedom, since the variable has a real part and an imaginary part. We now perform the following trick: instead of using the real and imaginary parts as the independent variables, we use an(t) and its complex conjugate
an*(t). With this choice of independent variables, we can calculate the partial derivative
By applying Schrödinger's equation and using the orthonormality of the basis states, this further reduces to
Similarly, one can show that
If we define "conjugate momentum" variables πn by
then the above equations become
which is precisely the form of Hamilton's equations, with the
s as the generalized coordinates, the 
s as the conjugate momenta, and 
taking the place of the classical Hamiltonian.
Quantum mechanics
Quantum mechanics, also known as quantum physics or quantum theory, is a branch of physics providing a mathematical description of much of the dual particle-like and wave-like behavior and interactions of energy and matter. It departs from classical mechanics primarily at the atomic and subatomic...
, the Hamiltonian H, also or Ĥ, is the operator
Operator (physics)
In physics, an operator is a function acting on the space of physical states. As a resultof its application on a physical state, another physical state is obtained, very often along withsome extra relevant information....
corresponding to the total energy
Energy
In physics, energy is an indirectly observed quantity. It is often understood as the ability a physical system has to do work on other physical systems...
of the system. Its spectrum is the set of possible outcomes when one measures the total energy of a system. Because of its close relation to the time-evolution of a system, it is of fundamental importance in most formulations of quantum theory.
Basic introduction
By analogy with classical mechanicsClassical mechanics
In physics, classical mechanics is one of the two major sub-fields of mechanics, which is concerned with the set of physical laws describing the motion of bodies under the action of a system of forces...
, the Hamiltonian is commonly expressed as the sum of operators corresponding to the kinetic
Kinetic energy
The kinetic energy of an object is the energy which it possesses due to its motion.It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its acceleration, the body maintains this kinetic energy unless its speed changes...
and potential
Potential energy
In physics, potential energy is the energy stored in a body or in a system due to its position in a force field or due to its configuration. The SI unit of measure for energy and work is the Joule...
energies of a system, in the form
(although this is not the technical definition of the Hamiltonian in classical mechanics
Hamiltonian mechanics
Hamiltonian mechanics is a reformulation of classical mechanics that was introduced in 1833 by Irish mathematician William Rowan Hamilton.It arose from Lagrangian mechanics, a previous reformulation of classical mechanics introduced by Joseph Louis Lagrange in 1788, but can be formulated without...
, it is the form it most commonly takes). The potential operator V typically takes the form of a function V(r,t) of position and time
Spacetime
In physics, spacetime is any mathematical model that combines space and time into a single continuum. Spacetime is usually interpreted with space as being three-dimensional and time playing the role of a fourth dimension that is of a different sort from the spatial dimensions...
, which simply acts on states as a multiplicative factor. The operator T corresponding to kinetic energy is constructed by analogy with the classical formula
with
the momentum and the mass.Schrödinger
Erwin Schrödinger
Erwin Rudolf Josef Alexander Schrödinger was an Austrian physicist and theoretical biologist who was one of the fathers of quantum mechanics, and is famed for a number of important contributions to physics, especially the Schrödinger equation, for which he received the Nobel Prize in Physics in 1933...
constructed his momentum operator
Momentum operator
In quantum mechanics, momentum is defined as an operator on the wave function. The Heisenberg uncertainty principle defines limits on how accurately the momentum and position of a single observable system can be known at once...
using the substitution
where
(NablaNabla
Nabla may refer to one of the following:* the nabla symbol, which is used to denote the mathematical del operator where tensor is formal.* Nabla , a Hebrew stringed instrument after which that symbol was named, see harp....
) is the gradient
Gradient
In vector calculus, the gradient of a scalar field is a vector field that points in the direction of the greatest rate of increase of the scalar field, and whose magnitude is the greatest rate of change....
operator, i is the unit imaginary number
Imaginary number
An imaginary number is any number whose square is a real number less than zero. When any real number is squared, the result is never negative, but the square of an imaginary number is always negative...
, and
is the reduced Planck constant. Combining this with the potential term yieldswhich allows one to apply the Hamiltonian to systems described by a wave function
.This is the approach commonly taken in introductory treatments of quantum mechanics, using the formalism of Schrödinger's wave mechanics. However, in the more general formalism
Bra-ket notation
Bra-ket notation is a standard notation for describing quantum states in the theory of quantum mechanics composed of angle brackets and vertical bars. It can also be used to denote abstract vectors and linear functionals in mathematics...
of Dirac
Paul Dirac
Paul Adrien Maurice Dirac, OM, FRS was an English theoretical physicist who made fundamental contributions to the early development of both quantum mechanics and quantum electrodynamics...
, the Hamiltonian is typically implemented as an operator on a Hilbert space
Hilbert space
The mathematical concept of a Hilbert space, named after David Hilbert, generalizes the notion of Euclidean space. It extends the methods of vector algebra and calculus from the two-dimensional Euclidean plane and three-dimensional space to spaces with any finite or infinite number of dimensions...
in the following way:
- The eigenkets (eigenvectors) of H, denoted
, provide an orthonormal basisOrthonormal basisIn mathematics, particularly linear algebra, an orthonormal basis for inner product space V with finite dimension is a basis for V whose vectors are orthonormal. For example, the standard basis for a Euclidean space Rn is an orthonormal basis, where the relevant inner product is the dot product of...
for the Hilbert space. The spectrum of allowed energy levels of the system is given by the set of eigenvalues, denoted {Ea}, solving the equation:
- Since H is a Hermitian operator, the energy is always a real numberReal numberIn mathematics, a real number is a value that represents a quantity along a continuum, such as -5 , 4/3 , 8.6 , √2 and π...
.
(From a mathematically rigorous point of view, care must be taken with the above assumptions. Operators on infinite-dimensional Hilbert spaces need not have eigenvalues (the set of eigenvalues does not necessarily coincide with the spectrum of an operator). However, all routine quantum mechanical calculations can be done using the physical formulation.)
Schrödinger equation
The Hamiltonian generates the timeTime
Time is a part of the measuring system used to sequence events, to compare the durations of events and the intervals between them, and to quantify rates of change such as the motions of objects....
evolution of quantum states. If
is the state of the system at time t, thenThis equation is known as the Schrödinger equation
Schrödinger equation
The Schrödinger equation was formulated in 1926 by Austrian physicist Erwin Schrödinger. Used in physics , it is an equation that describes how the quantum state of a physical system changes in time....
. (It takes the same form as the Hamilton–Jacobi equation
Hamilton–Jacobi equation
In mathematics, the Hamilton–Jacobi equation is a necessary condition describing extremal geometry in generalizations of problems from the calculus of variations. In physics, the Hamilton–Jacobi equation is a reformulation of classical mechanics and, thus, equivalent to other formulations such as...
, which is one of the reasons H is also called the Hamiltonian.) Given the state at some initial time (t = 0), we can integrate it to obtain the state at any subsequent time. In particular, if H is independent of time, then
The exponential
Matrix exponential
In mathematics, the matrix exponential is a matrix function on square matrices analogous to the ordinary exponential function. Abstractly, the matrix exponential gives the connection between a matrix Lie algebra and the corresponding Lie group....
operator on the right hand side of the Schrödinger equation is usually defined by the corresponding power series in H. One might notice that taking polynomials or power series of unbounded operator
Unbounded operator
In mathematics, more specifically functional analysis and operator theory, the notion of unbounded operator provides an abstract framework for dealing with differential operators, unbounded observables in quantum mechanics, and other cases....
s that are not defined everywhere may not make mathematical sense. Rigorously, to take functions of unbounded operators, a functional calculus
Functional calculus
In mathematics, a functional calculus is a theory allowing one to apply mathematical functions to mathematical operators. It is now a branch of the field of functional analysis, connected with spectral theory. In mathematics, a functional calculus is a theory allowing one to apply mathematical...
is required. In the case of the exponential function, the continuous
Continuous functional calculus
In mathematics, the continuous functional calculus of operator theory and C*-algebra theory allows applications of continuous functions to normal elements of a C*-algebra. More precisely,Theorem...
, or just the holomorphic functional calculus
Holomorphic functional calculus
In mathematics, holomorphic functional calculus is functional calculus with holomorphic functions. That is to say, given a holomorphic function ƒ of a complex argument z and an operator T, the aim is to construct an operatorf\,...
suffices. We note again, however, that for common calculations the physicists' formulation is quite sufficient.
By the *-homomorphism
Homomorphism
In abstract algebra, a homomorphism is a structure-preserving map between two algebraic structures . The word homomorphism comes from the Greek language: ὁμός meaning "same" and μορφή meaning "shape".- Definition :The definition of homomorphism depends on the type of algebraic structure under...
property of the functional calculus, the operator
is a unitary operator
Unitary operator
In functional analysis, a branch of mathematics, a unitary operator is a bounded linear operator U : H → H on a Hilbert space H satisfyingU^*U=UU^*=I...
. It is the time evolution
Time evolution
Time evolution is the change of state brought about by the passage of time, applicable to systems with internal state . In this formulation, time is not required to be a continuous parameter, but may be discrete or even finite. In classical physics, time evolution of a collection of rigid bodies...
operator, or propagator, of a closed quantum system. If the Hamiltonian is time-independent, {U(t)} form a one parameter unitary group
Stone's theorem on one-parameter unitary groups
In mathematics, Stone's theorem on one-parameter unitary groups is a basic theorem of functional analysis which establishes a one-to-one correspondence between self-adjoint operators on a Hilbert space H and one-parameter families of unitary operators...
(more than a semigroup); this gives rise to the physical principle of detailed balance
Detailed balance
The principle of detailed balance is formulated for kinetic systems which are decomposed into elementary processes : At equilibrium, each elementary process should be equilibrated by its reverse process....
.
Energy eigenket degeneracy, symmetry, and conservation laws
In many systems, two or more energy eigenstates have the same energy. A simple example of this is a free particle, whose energy eigenstates have wavefunctions that are propagating plane waves. The energy of each of these plane waves is inversely proportional to the square of its wavelengthWavelength
In physics, the wavelength of a sinusoidal wave is the spatial period of the wave—the distance over which the wave's shape repeats.It is usually determined by considering the distance between consecutive corresponding points of the same phase, such as crests, troughs, or zero crossings, and is a...
. A wave propagating in the x direction is a different state from one propagating in the y direction, but if they have the same wavelength, then their energies will be the same. When this happens, the states are said to be degenerate.
It turns out that degeneracy occurs whenever a nontrivial unitary operator U commutes with the Hamiltonian. To see this, suppose that
is an energy eigenket. Then is an energy eigenket with the same eigenvalue, sinceSince U is nontrivial, at least one pair of
and must represent distinct states. Therefore, H has at least one pair of degenerate energy eigenkets. In the case of the free particle, the unitary operator which produces the symmetry is the rotation operator, which rotates the wavefunctions by some angle while otherwise preserving their shape.The existence of a symmetry operator implies the existence of a conserved
Conservation law
In physics, a conservation law states that a particular measurable property of an isolated physical system does not change as the system evolves....
observable. Let G be the Hermitian generator of U:
It is straightforward to show that if U commutes with H, then so does G:
Therefore,
In obtaining this result, we have used the Schrödinger equation, as well as its dual
Bra-ket notation
Bra-ket notation is a standard notation for describing quantum states in the theory of quantum mechanics composed of angle brackets and vertical bars. It can also be used to denote abstract vectors and linear functionals in mathematics...
,
Thus, the expected value
Expected value
In probability theory, the expected value of a random variable is the weighted average of all possible values that this random variable can take on...
of the observable G is conserved for any state of the system. In the case of the free particle, the conserved quantity is the angular momentum
Angular momentum
In physics, angular momentum, moment of momentum, or rotational momentum is a conserved vector quantity that can be used to describe the overall state of a physical system...
.
Hamilton's equations
HamiltonWilliam Rowan Hamilton
Sir William Rowan Hamilton was an Irish physicist, astronomer, and mathematician, who made important contributions to classical mechanics, optics, and algebra. His studies of mechanical and optical systems led him to discover new mathematical concepts and techniques...
's equations in classical Hamiltonian mechanics
Hamiltonian mechanics
Hamiltonian mechanics is a reformulation of classical mechanics that was introduced in 1833 by Irish mathematician William Rowan Hamilton.It arose from Lagrangian mechanics, a previous reformulation of classical mechanics introduced by Joseph Louis Lagrange in 1788, but can be formulated without...
have a direct analogy in quantum mechanics. Suppose we have a set of basis states
, which need not necessarily be eigenstates of the energy. For simplicity, we assume that they are discrete, and that they are orthonormal, i.e.,Note that these basis states are assumed to be independent of time. We will assume that the Hamiltonian is also independent of time.
The instantaneous state of the system at time t,
, can be expanded in terms of these basis states:where
The coefficients an(t) are complex
Complex number
A complex number is a number consisting of a real part and an imaginary part. Complex numbers extend the idea of the one-dimensional number line to the two-dimensional complex plane by using the number line for the real part and adding a vertical axis to plot the imaginary part...
variables. We can treat them as coordinates which specify the state of the system, like the position and momentum coordinates which specify a classical system. Like classical coordinates, they are generally not constant in time, and their time dependence gives rise to the time dependence of the system as a whole.
The expectation value of the Hamiltonian of this state, which is also the mean energy, is
where the last step was obtained by expanding
in terms of the basis states.Each of the an(t)s actually corresponds to two independent degrees of freedom, since the variable has a real part and an imaginary part. We now perform the following trick: instead of using the real and imaginary parts as the independent variables, we use an(t) and its complex conjugate
Complex conjugate
In mathematics, complex conjugates are a pair of complex numbers, both having the same real part, but with imaginary parts of equal magnitude and opposite signs...
an*(t). With this choice of independent variables, we can calculate the partial derivative
Partial derivative
In mathematics, a partial derivative of a function of several variables is its derivative with respect to one of those variables, with the others held constant...
By applying Schrödinger's equation and using the orthonormality of the basis states, this further reduces to
Similarly, one can show that
If we define "conjugate momentum" variables πn by
then the above equations become
which is precisely the form of Hamilton's equations, with the
s as the generalized coordinates, the s as the conjugate momenta, and taking the place of the classical Hamiltonian.