The overlap matrix is a square matrix, used in quantum chemistry to describe the inter-relationship of a set of basis vectors of a quantum system. In particular, if the vectors are orthogonal to one another, the overlap matrix will be diagonal. In addition, if the basis vectors form an orthonormal set, the overlap matrix will be the identity matrix. The overlap matrix is always n×n, where n is the number of basis functions used. It is a kind of Gramian matrix.
In general, the overlap matrix is defined as:
where
- is the j-th basis ket (vector), and
- is the j-th wavefunction, defined as :.
In particular, if the set is normalized (though not necessarily orthogonal) then the diagonal elements will be identically 1 and the magnitude of the off-diagonal elements less than or equal to one with equality if and only if there is linear dependence in the basis set as per the Cauchy–Schwarz inequality. Moreover, the matrix is always positive definite; that is to say, the eigenvalues are all strictly positive.
Famous quotes containing the words overlap and/or matrix:
“A lady is nothing very specific. One man’s lady is another man’s woman; sometimes, one man’s lady is another man’s wife. Definitions overlap but they almost never coincide.”
—Russell Lynes (b. 1910)
““The matrix is God?”
“In a manner of speaking, although it would be more accurate ... to say that the matrix has a God, since this being’s omniscience and omnipotence are assumed to be limited to the matrix.”
“If it has limits, it isn’t omnipotent.”
“Exactly.... Cyberspace exists, insofar as it can be said to exist, by virtue of human agency.””
—William Gibson (b. 1948)