If Hq is chosen wisely, then the perturbation is small and the perturbation expansion (i.e., the sum of the 1st, 2nd,. .., nth-order energies) converges quickly. To obtain a perturbation expansion for the correlation energy, the best way is to choose the Hartree-Fock Hamiltonian as the zeroth-order Hamiltonian. The application to N-electron molecular systems is sometimes called Mpller-Plesset (MP) perturbation theory. These methods, which can be terminated at second (MP2), third (MP3), or fourth order (MP4), with these three being the most frequently used in different ab initio programs, calculate the correlation energy and rely on a good description of the virtual orbitals in the original SCF function. The calculated total correlation energy is therefore quite dependent on the quality of the basis set. [Pg.41]

HyperChem supports MP2 (second order Mpller-Plesset) correlation energy calculationsusing afe mi/io methods with anyavailable basis set. In order to save main memory and disk space, the HyperChem MP2 electron correlation calculation normally uses a so called frozen-core approximation, i.e. the inner shell (core) orbitals are omitted. A setting in CHEM.INI allows excitations from the core orbitals to be included if necessary (melted core). Only the single point calculation is available for this option. [Pg.41]

Another approach to electron correlation is Moller-Plesset perturbation theory. Qualitatively, Moller-Plesset perturbation theory adds higher excitations to Hartree-Fock theory as a non-iterative correction, drawing upon techniques from the area of mathematical physics known as many body perturbation theory. [Pg.267]

F is the Fock operator acting on the i electron. [Pg.268]

Since the y s are orthonormal, the inner product of any with itself is one, and the inner product of any distinct two of them is 0. [Pg.269]

The two factors in the numerator of the first expression in the second line are one another s complex conjugates, and so reduce to the square of its modulus in the final expression. [Pg.271]

In addition, the numerator will be nonzero only for double substitutions. Single substitutions are known to make this expression zero by Brillouin s theorem. Triple and higher substitutions also result in zero value since the Hamiltonian contains only one and two-electron terms (physically, this means that all interactions between electrons occur pairwise). [Pg.271]

the value of E the first perturbation to the Hartree-Fock energy, will always be negative. Lowering the energy is what the exact correction should do, although the Moller-Plesset perturbation theory correction is capable of overcorrecting it, since it is not variational (and higher order corrections may be positive). [Pg.271]

By a similar although more elaborate process, the third and fourth order energy corrections can be derived. For further details, consult the references. [Pg.271]

Molecular systems, description, 106 Molecular theory, structure and transport, 258-266 Molecules, LDF theory, 49-66 Moller-Plesset perturbation theory use, 346 [Pg.431]

To obtain an improvement on the Hartree-Fock energy it is therefore necessary to use Moller-Plesset perturbation theory to at least second order. This level of theory is referred to as MP2 and involves the integral J dr. The higher-order wavefunction g is [Pg.135]

This Foek operator is used to define the unperturbed Hamiltonian of Moller-Plesset perturbation theory (MPPT) [Pg.579]

A number of types of calculations begin with a HF calculation and then correct for correlation. Some of these methods are Moller-Plesset perturbation theory (MPn, where n is the order of correction), the generalized valence bond (GVB) method, multi-conhgurational self-consistent held (MCSCF), conhgu-ration interaction (Cl), and coupled cluster theory (CC). As a group, these methods are referred to as correlated calculations. [Pg.22]

Correlation can be added as a perturbation from the Hartree-Fock wave function. This is called Moller-Plesset perturbation theory. In mapping the HF wave function onto a perturbation theory formulation, HF becomes a hrst-order perturbation. Thus, a minimal amount of correlation is added by using the second-order MP2 method. Third-order (MP3) and fourth-order (MP4) calculations are also common. The accuracy of an MP4 calculation is roughly equivalent to the accuracy of a CISD calculation. MP5 and higher calculations are seldom done due to the high computational cost (A time complexity or worse). [Pg.22]

MP2 2 Order Moller-Plesset Perturbation Theory Through 2nd derivatives [Pg.9]

MP4 4 Order Moller-Plesset Perturbation Theory (including Singles, Doubles, Triples and Quadruples by default) Energies only [Pg.9]

MoUer-Plesset perturbation theory energies through fifth-order (accessed via the keywords MP2, MP3, MP4, and MP5), optimizations via analytic gradients for second-order (MP2), third-order (MP3) and fourth-order (without triples MP4SDQ), and analytic frequencies for second-order (MP2). [Pg.114]

Electron correlation (how well does MoUer-Plesset perturbation theory converge for these problems ) [Pg.187]

So far, we ve presented only general perturbation theory results.We U now turn to the particular case of Moller-Plesset perturbation theory. Here, Hg is defined as the sum of the one-electron Fock operators [Pg.268]

Things have moved on since the early papers given above. The development of Mpller-Plesset perturbation theory (Chapter 11) marked a turning point in treatments of electron correlation, and made such calculations feasible for molecules of moderate size. The Mpller-Plesset method is usually implemented up to MP4 but the convergence of the MPn series is sometimes unsatisfactory. The effect [Pg.321]

MPn (Mdller-Plesset Perturbation Theory to Order n) 200, 206, 321 Mulliken polulation indices 182 Mulliken population analysis 229, 316 Multiple minima 52 Multipole expansion 270 Multipole moment 269 Mutual potential energy 27, 62 [Pg.334]

Coupled cluster is closely connected with Mpller-Plesset perturbation theory, as mentioned at the start of this section. The infinite Taylor expansion of the exponential operator (eq. (4.46)) ensures that the contributions from a given excitation level are included to infinite order. Perturbation theory indicates that doubles are the most important, they are the only contributors to MP2 and MP3. At fourth order, there are contributions from singles, doubles, triples and quadruples. The MP4 quadruples [Pg.137]

Perturbation theory basis for RB and RBST potentials, 179 computation of correlation energies, 207 See also Moller-Plesset perturbation theory [Pg.432]

Highest occupied molecular orbital Intermediate neglect of differential overlap Linear combination of atomic orbitals Local density approximation Local spin density functional theory Lowest unoccupied molecular orbital Many-body perturbation theory Modified INDO version 3 Modified neglect of diatomic overlap Molecular orbital Moller-Plesset [Pg.124]

A Moeller-Plesset Cl correction to v / is based on perturbation theory, by which the Hamiltonian is expressed as a Hartree-Fock Hamiltonian perturbed by a small perturbation operator P through a minimization constant X [Pg.313]

© 2019 chempedia.info