Coupled Cluster Theory: Size Consistency

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Description

This lecture covers the Coupled Cluster theory, focusing on the expansion of the perturbed wavefunction in doubly excited Slater determinants and the second-order correction to the energy. It discusses Size Extensivity and Size Consistency, post-Hartree-Fock methods like Configuration Interaction and Coupled Cluster Theory, and why truncated Configuration Interaction is not size-consistent.

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Related lectures (13)

Related concepts (89)

Configuration interaction

Configuration interaction (CI) is a post-Hartree–Fock linear variational method for solving the nonrelativistic Schrödinger equation within the Born–Oppenheimer approximation for a quantum chemical multi-electron system. Mathematically, configuration simply describes the linear combination of Slater determinants used for the wave function. In terms of a specification of orbital occupation (for instance, (1s)2(2s)2(2p)1...), interaction means the mixing (interaction) of different electronic configurations (states).

Multi-configurational self-consistent field

Multi-configurational self-consistent field (MCSCF) is a method in quantum chemistry used to generate qualitatively correct reference states of molecules in cases where Hartree–Fock and density functional theory are not adequate (e.g., for molecular ground states which are quasi-degenerate with low-lying excited states or in bond-breaking situations). It uses a linear combination of configuration state functions (CSF), or configuration determinants, to approximate the exact electronic wavefunction of an atom or molecule.

Electronic correlation

Electronic correlation is the interaction between electrons in the electronic structure of a quantum system. The correlation energy is a measure of how much the movement of one electron is influenced by the presence of all other electrons. Within the Hartree–Fock method of quantum chemistry, the antisymmetric wave function is approximated by a single Slater determinant. Exact wave functions, however, cannot generally be expressed as single determinants.

Coupled cluster

Coupled cluster (CC) is a numerical technique used for describing many-body systems. Its most common use is as one of several post-Hartree–Fock ab initio quantum chemistry methods in the field of computational chemistry, but it is also used in nuclear physics. Coupled cluster essentially takes the basic Hartree–Fock molecular orbital method and constructs multi-electron wavefunctions using the exponential cluster operator to account for electron correlation. Some of the most accurate calculations for small to medium-sized molecules use this method.

Polygon

In geometry, a polygon (ˈpɒlɪɡɒn) is a plane figure made up of line segments connected to form a closed polygonal chain. The segments of a closed polygonal chain are called its edges or sides. The points where two edges meet are the polygon's vertices or corners. An n-gon is a polygon with n sides; for example, a triangle is a 3-gon. A simple polygon is one which does not intersect itself. More precisely, the only allowed intersections among the line segments that make up the polygon are the shared endpoints of consecutive segments in the polygonal chain.