Stationary state

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In quantum mechanics, a stationary state is an eigenstate of a Hamiltonian, or in other words, a state of definite energy. It is called stationary because the corresponding probability density has no time dependence.

As an eigenstate of the Hamiltonian, a stationary state is not subject to change or decay (to a lower energy state). In practice, stationary states are never truly "stationary" for all time. Rather, they refer to the eigenstate of a Hamiltonian where small perturbative effects have been ignored. The language allows one to discuss the eigenstates of the unperturbed Hamiltonian, whereas the perturbation will eventually cause the stationary state to decay. The only true stationary state is the ground state.

[edit] Ground state

The ground state of a quantum mechanical system is its lowest-energy state. An excited state is any state with energy greater than the ground state. The ground state of a quantum field theory is usually called the vacuum state or the vacuum.

If more than one ground state exists, they are said to be degenerate. Many systems have degenerate ground states, for example, the hydrogen atom. It turns out that degeneracy occurs whenever a nontrivial unitary operator commutes with the Hamiltonian of the system.

According to the third law of thermodynamics, a system at absolute zero temperature exists in its ground state; thus, its entropy is determined by the degeneracy of the ground state. Many systems, such as a perfect crystal lattice, have a unique ground state and therefore have zero entropy at absolute zero (because ln(1) = 0).

In the approximation that the electrons do not interact, an atom, ion, or molecule is in its ground state when all of its electrons are in their lowest possible energy levels. When an atom is in its ground state, its electrons fill the lowest energy orbitals completely before they begin to occupy higher energy orbitals, and they fill subshells usually in accordance with Hund's rule. When we allow the electrons to interact, and treat them in a many-bodied way, then the ground state is simply the lowest energy state.