Closely approximating second-order Mo/ller–Plesset perturbation theory with a local triatomics in molecules model

Abstract

Articles you may be interested in NMR shielding tensors for density fitted local second-order Møller-Plesset perturbation theory using gauge including atomic orbitals J. Chem. Phys. 137, 084107 (2012); 10.1063/1.4744102Orbital-dependent correlation energy in density-functional theory based on a second-order perturbation approach: Success and failure Explicitly correlated second-order Møller-Plesset methods with auxiliary basis sets Second order Mo/ller-Plesset perturbation theory without basis set superposition error A new ansatz for local electron correlation is introduced, which truncates double substitutions subject to a triatomics in molecules ͑TRIM͒ criterion. TRIM includes all double substitutions in which one occupied-virtual substitution is atomic while the other substitution can be nonlocal ͑a cubic number, before cutoffs͒. With an additional approximation, the TRIM second-order Mo "llerPlesset perturbation theory ͑MP2͒ model can be noniteratively solved; this is the model that is implemented. Results are shown for absolute energies of alkane and polyene chains, rotational barriers of substituted ethylenes and benzenes, and association energies of the water and neon dimers. Over 99.7% of the untruncated MP2 energy is recovered for the test cases, and the relative energies of small systems are in error by less than 0.1 kcal/mol. By contrast, a diatomics in molecules ͑DIM͒ truncation recovers about 95% of the full MP2 energy, and yields errors several times larger for relative energies.

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

“…Indeed, the main disadvantage of wave function based correlated methods is the high scaling of the computational cost with the size of the system. Local correlation methods, [375][376][377][378][379][380][381][382][383] allow exploiting the fundamental local character of dynamical electron correlation, leading to methods that may scale linearly with the size of the system and thus largely reducing the computational costs of post-Hartree-Fock methods. As already anticipated in section 4.1, it is worth mentioning that local-MP2 has been implemented for extended systems by exploiting the translational and point symmetry poperties of crystalline structures 384 with the periodic boundary conditions as implemented in the CRYSCOR program, 328 and in the VASP program 330 through the random phase approximation associated to exact exchange.…”

Auxiliary basis expansions for large-scale electronic structure calculations

“…With the success of linear scaling methods (4,6,31,32) and local correlation models (33)(34)(35) for reducing the scaling with molecular size, it is desirable to combine them with the reduced prefactors offered by the auxiliary basis approach to produce still more efficient algorithms (22,23). The locality of the coefficients determines the extent to which low-scaling methods involving auxiliary basis expansions are possible without further approximations, such as fitting domains (22,23).…”

Geminal model chemistry II. Perturbative corrections

“…These studies were pioneered by Pulay and Saebø 26 -28 in the context of Møller-Plesset perturbation theory, and further developed using the coupled-cluster formalism. 29,30 The alternative localization schemes based on assignments of basis functions to individual nuclei are developed by Head-Gordon et al 31 The SSG theory bridges these two directions of research. The grouping of all orbitals into geminal subspaces is performed variationally, and is based on the strength of electron interactions between electrons on different orbitals.…”