Mpller-Plesset perturbation

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... 

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... 

Niu, S., Hall, M. B., 1997, Comparison of Hartree-Fock, Density Functional, Mpller-Plesset Perturbation, Coupled Cluster, and Configuration Interaction Methods for the Migratory Insertion of Nitric Oxide into a Cobalt-Carbon Bond , J. Phys. Chem. A, 101, 1360. 

The difference between the Hartree-Fock energy and the exact solution of the Schrodinger equation (Figure 60), the so-called correlation energy, can be calculated approximately within the Hartree-Fock theory by the configuration interaction method (Cl) or by a perturbation theoretical approach (Mpller-Plesset perturbation calculation wth order, MPn). Within a Cl calculation the wave function is composed of a linear combination of different Slater determinants. Excited-state Slater determinants are then generated by exciting electrons from the filled SCF orbitals to the virtual ones ... 

H. J. Werner, F. R. Manby, and P. J. Knowles, Fast linear scaling second order Mpller Plesset perturbation theory (MP2) using local and density fitting approximations. J. Chem. Phys. 118, 8149 8160 (2003). 

A series of single-point energy calculations is carried out at higher levels of theory. The first higher-level calculation is the complete fourth-order Mpller-Plesset perturbation theory [13] with the 6-31G(d) basis set, i.e. MP4/6-31G(d). For convenience of notation, we represent this as MP4/d. This energy is then modified by a series of corrections from additional calculations ... 

There is also a hierarchy of electron correlation procedures. The Hartree-Fock (HF) approximation neglects correlation of electrons with antiparallel spins. Increasing levels of accuracy of electron correlation treatment are achieved by Mpller-Plesset perturbation theory truncated at the second (MP2), third (MP3), or fourth (MP4) order. Further inclusion of electron correlation is achieved by methods such as quadratic configuration interaction with single, double, and (perturbatively calculated) triple excitations [QCISD(T)], and by the analogous coupled cluster theory [CCSD(T)] [8],... 

In SOPPA [5] a Mpller-Plesset perturbation theory expansion of the wave function [28,48] is employed ... 

Very accurate values of the dipole and quadrupole polarizability for the equilibrium internuclear distance of HF can be found in a review article by Maroulis [71], calculated with finite-field Mpller-Plesset perturbation theory at various orders and coupled cluster theory using a carefully selected basis set. 

In Eq. (87) the equality sign holds for a pure state of a two-electron system. In terms of Mpller-Plesset perturbation theory (see Section V. D) one gets, independently of n [24, 25],... 

D. Cremer, Mpller-Plesset perturbation theory, in Encyclopedia ( Computational Chemistry P. von Rague Schleyer, N. L. Allinger, T. Clark, J. Gasteiger, P. A. Kollman, H. E. Schaefer, and P. R. Schreiner, eds., Wiley, Hoboken, NJ, 1998, pp. 1706-1735. 

The calculations are not all at exactly the same bond length R. The basis set is indicated after the slash in the method. R, L, C, and T are basis sets of Slater-type functions. The aug-cc-pVDZ and aug-cc-pVTZ basis sets [360] are composed of Gaussian functions. SCF stands for self-consistent-field MC, for multiconfiguration FO, for first-order Cl, for configuration interaction MR, for multireference MPn, for nth-order Mpller-Plesset perturbation theory and SDQ, for singles, doubles, and quadruples. 

H2O molecules at different positions. Second-ordCT Mpller-Plesset perturbation theory (MP2) with a 6-311- -G(d,p) basis set has also been apphed to the study of ONO—O, (H20) (n = 1 or 2) complexes. Koppenol and Klasinc studied the cis and trans con-formers as well as the transition state for torsional motion of ONO—O at the HF/6-31(d) leveP. In their calculations, the trans conformer is slightly more stable than the cis form, and the rotational barrier was thought to be quite high. However, correlated methods (MP2) were also used to study this molecule, and they predict that the cis conformer is more stable than the trans conformer . ... 

The Section on More Quantitive Aspects of Electronic Structure Calculations introduces many of the computational chemistry methods that are used to quantitatively evaluate molecular orbital and configuration mixing amplitudes. The Hartree-Fock self-consistent field (SCF), configuration interaction (Cl), multiconfigurational SCF (MCSCF), many-body and Mpller-Plesset perturbation theories,... 

This Fock operator is used to define the unperturbed Hamiltonian of Mpller-Plesset perturbation theory (MPPT) ... 

In ab initio methods the HER approximation is used for build-up of initial estimate for and which have to be further improved by methods of configurational interaction in the complete active space (CAS) [39], or by Mpller-Plesset perturbation theory (MPn) of order n, or by the coupled clusters [40,41] methods. In fact, any reasonable result within the ab initio QC requires at least minimal involvement of electron correlation. All the technical tricks invented to go beyond the HFR calculation scheme in terms of different forms of the trial wave function or various perturbative procedures represent in fact attempts to estimate somehow the second term of Eq. (5) - the cumulant % of the two-particle density matrix. 

All of the systems were initially optimized using a much higher level of theory, in order to ensure that the OM2 method provides a realistic description of the structure. The method employed was the second-order Mpller-Plesset perturbation theory (MP2) [50] using the cc-pVDZ basis set [51]. The resolution-of-identity (RI) approximation for the evaluation of the electron-repulsion integrals implemented in Turbomole was utilized [52]. 

The other area in which projection of an unrestricted result has received attention is projected Mpller-Plesset perturbation theory, the PUMPn methods [31], where n is the order of the perturbation theory. In cases in which the UHF approximation is a poor starting point (considerable spin contamination, for example), the convergence of the MP perturbation expansion can be slow and/or erratic. The PUMP methods apply projection operators to the perturbation expansion, although usually not full projection but simply annihilation of the leading contaminants. This approach has met with mixed success again, it represents a rather expensive modification to a technique that was originally chosen partly for its economy — seldom a recipe for success. 

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