相关论文: Comprehensive Analysis of the Neglect of Diatomic …
Semiempirical molecular orbital (SEMO) models based on the neglect of diatomic differential overlap (NDDO) approximation efficiently solve the self-consistent field equations by rather drastic approximations. The computational efficiency…
We apply the analytically solvable model of two electrons in two orbitals to diradical molecules, characterized by two unpaired electrons. The effect of the doubly occupied and empty orbitals is taken into account by means of random phase…
Favorably scaling numerical time-dependent many-electron techniques such as time-dependent density functional theory (TDDFT) with adiabatic exchange-correlation potentials typically fail in capturing highly correlated electron dynamics. We…
Low-scaling electron correlation theory based on the pair natural orbital approximation, PNO-CCSD(T), has become a powerful computational tool. Motivated by the recent discovery of large errors for organometallic molecules, we assess the…
In the present article, we show how to formulate the partially contracted n-electron valence second order perturbation theory (NEVPT2) energies in the atomic and active molecular orbital basis by employing the Laplace transformation of…
A method for increasing the accuracy of configuration interaction (CI) calculations of molecules and other electronic systems is proposed. The energy defect of a given calculation is associated with the electron pair origin of…
In this work we explore the performance of approximations to electron correlation in reduced density-matrix functional theory (RDMFT) and of approximations to the observables calculated within this theory. Our analysis focuses on the…
This chapter provides a comprehensive review of fundamental concepts related to approximate natural orbital functionals (NOFs), emphasizing their significance in quantum chemistry and physics. Focusing on fermions, the discussion excludes…
MNDO-based semiempirical methods in quantum chemistry have found widespread application in the modelling of large and complex systems. A method for the analytic evaluation of first and second derivatives of molecular properties against…
In a previous paper, I demonstrated the accuracy of simple, precessing, power ellipse (p-ellipse) approximations to orbits of low-to-moderate eccentricity in power-law potentials. Here I explore several extensions of these approximations to…
We extend to strongly correlated molecular systems the recently introduced basis-set incompleteness correction based on density-functional theory (DFT) [E. Giner et al., J. Chem. Phys. 149, 194301 (2018)]. This basis-set correction relies…
The nuclear-electronic orbital (NEO) method is a well-established approach for treating nuclei quantum mechanically in molecular systems beyond the usual Born-Oppenheimer approximation. In this work, we present a strategy to implement the…
A fully analytical approximation for the observable characteristics of many-electron atoms is developed via a complete and orthonormal hydrogen-like basis with a single-effective charge parameter for all electrons of a given atom. The basis…
The state-of-the art proof of a global inf-sup condition on mixed finite element schemes does not allow for an analysis of truly indefinite, second-order linear elliptic PDEs. This paper, therefore, first analyses a nonconforming finite…
Molecule-optimized basis sets, based on approximate natural orbitals, are developed for accelerating the convergence of quantum calculations with strongly correlated (multi-referenced) electrons. We use a low-cost approximate solution of…
Plane-wave electronic-structure predictions based upon orbital-dependent density-functional theory (OD-DFT) approximations, such as hybrid density-functional methods and self-interaction density-functional corrections, are severely affected…
The original formulation (Phys. Rev. Lett. 119, 063002, 2017) of the natural orbital functional - second-order M{\o}ller-Plesset (NOF-MP2) method is based on the MP2 that uses the canonical Hartree-Fock molecular orbitals. The current work…
We review the simple linear muffin-tin orbital method in the atomic-spheres approximation and a tight-binding representation (TB-LMTO-ASA method), and show how it can be generalized to an accurate and robust Nth order muffin-tin orbital…
This contribution proposes novel data-driven surrogate modeling approaches for parameterized parabolic PDEs, where the parameter dependence can be split into two parts with different decay behavior of the Kolmogorov $N$-width. Such problems…
We use projector operators to correct the Kohn-Sham Hamiltonian of density functional theory (KS-DFT) so that the resulting mean-field scheme yields, in finite systems, virtual orbitals and energy gaps in better agreement with those…