Publication

Variational optimization of effective atom centered potentials for molecular properties

Ursula Röthlisberger, Ivano Tavernelli, Anatole von Lilienfeld
2005
Journal Articles

Abstract

In plane wave based electronic structure calcns. the interaction of core and valence electrons is usually represented by at. effective core potentials. They are constructed in such a way that the shape of the at. valence orbitals outside a certain core radius is reproduced correctly with respect to the corresponding all-electron calcns. Here we present a method which, in conjunction with d. functional perturbation theory, allows to optimize effective core potentials in order to reproduce ground-state mol. properties from arbitrarily accurate ref. calcns. within std. d. functional calcns. We demonstrate the wide range of possible applications in theor. chem. of such optimized effective core potentials (OECPs) by means of two examples. We first use OECPs to tackle the link atom problem in quantum mechanics/mol. mechanics (QM/MM) schemes proposing a fully automatized procedure for the design of link OECPs, which are designed in such a way that they minimally perturb the electronic structure in the QM region. In the second application, we use OECPs in two sample mols. (water and acetic acid) such as to reproduce electronic densities and derived mol. properties of hybrid (B3LYP) quality within general gradient approximated (BLYP) d. functional calcns. [on SciFinder (R)]

Official source

https://infoscience.epfl.ch/entities/publication/6b25693a-f105-429c-be86-d57125a6ebc2

About this result

This page is automatically generated and may contain information that is not correct, complete, up-to-date, or relevant to your search query. The same applies to every other page on this website. Please make sure to verify the information with EPFL's official sources.

Ursula Röthlisberger, Ivano Tavernelli, Anatole von Lilienfeld
2005
Journal Articles

Abstract

Official source

https://infoscience.epfl.ch/entities/publication/6b25693a-f105-429c-be86-d57125a6ebc2

About this result

Related concepts (32)

Density functional theory

Density-functional theory (DFT) is a computational quantum mechanical modelling method used in physics, chemistry and materials science to investigate the electronic structure (or nuclear structure) (principally the ground state) of many-body systems, in particular atoms, molecules, and the condensed phases. Using this theory, the properties of a many-electron system can be determined by using functionals, i.e. functions of another function. In the case of DFT, these are functionals of the spatially dependent electron density.

Valence bond theory

In chemistry, valence bond (VB) theory is one of the two basic theories, along with molecular orbital (MO) theory, that were developed to use the methods of quantum mechanics to explain chemical bonding. It focuses on how the atomic orbitals of the dissociated atoms combine to give individual chemical bonds when a molecule is formed. In contrast, molecular orbital theory has orbitals that cover the whole molecule. In 1916, G. N. Lewis proposed that a chemical bond forms by the interaction of two shared bonding electrons, with the representation of molecules as Lewis structures.

Valence electron

In chemistry and physics, a valence electron is an electron in the outer shell associated with an atom, and that can participate in the formation of a chemical bond if the outer shell is not closed. In a single covalent bond, a shared pair forms with both atoms in the bond each contributing one valence electron. The presence of valence electrons can determine the element's chemical properties, such as its valence—whether it may bond with other elements and, if so, how readily and with how many.

Related publications (32)

Encoding quantum-chemical knowledge into machine-learning models of complex molecular properties

Ksenia Briling

Statistical (machine-learning, ML) models are more and more often used in computational chemistry as a substitute to more expensive ab initio and parametrizable methods. While the ML algorithms are capable of learning physical laws implicitly from data, ad ...

EPFL2024

Efficient and insightful descriptors for representing molecular and material space

Alexander Jan Goscinski

Data-driven approaches have been applied to reduce the cost of accurate computational studies on materials, by using only a small number of expensive reference electronic structure calculations for a representative subset of the materials space, and using ...

EPFL2024

Orbital-Resolved DFT plus U for Molecules and Solids

Nicola Marzari, Iurii Timrov, Eric Macke

We present an orbital-resolved extension of the Hubbard U correction to density-functional theory (DFT). Compared to the conventional shell-averaged approach, the prediction of energetic, electronic and structural properties is strongly improved, particula ...

Amer Chemical Soc2024