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Computing saddle points with a prescribed Morse index on potential energy surfaces is crucial for characterizing transition states for nosie-induced rare transition events in physics and chemistry. Many numerical algorithms for this type of…

Optimization and Control · Mathematics 2025-01-28 Shuting Gu , Hao Zhang , Xiaoqun Zhang , Xiang Zhou

We investigate an extension of excited state mean-field theory in which the energy expression is augmented with density functional components in an effort to include the effects of weak electron correlations. The approach remains…

Chemical Physics · Physics 2020-02-05 Luning Zhao , Eric Neuscamman

We analytically construct the wave function that, for a given initial state, produces a prescribed density for a quantum ring with two non-interacting particles in a singlet state. In this case the initial state is completely determined by…

Strongly Correlated Electrons · Physics 2013-08-23 M. Ruggenthaler , S. E. B. Nielsen , R. van Leeuwen

Localized molecular orbitals are often used for the analysis of chemical bonds, but they can also serve to efficiently and comprehensibly compute linear response properties. While conventional canonical molecular orbitals provide an…

Chemical Physics · Physics 2023-02-08 Souloke Sen , Bruno Senjean , Lucas Visscher

A central challenge to many fields of science and engineering involves minimizing non-convex error functions over continuous, high dimensional spaces. Gradient descent or quasi-Newton methods are almost ubiquitously used to perform such…

Machine Learning · Computer Science 2014-05-29 Razvan Pascanu , Yann N. Dauphin , Surya Ganguli , Yoshua Bengio

Based on the work of Gorling and that of Levy and Nagy, density-functional formalism for many Fermionic excited-states is explored through a careful and rigorous analysis of the excited-state density to external potential mapping. It is…

Materials Science · Physics 2009-11-11 Prasanjit Samal , Manoj K. Harbola

We introduce and benchmark a systematically improvable route for excited-state calculations, state-specific configuration interaction ($\Delta$CI), \alert{which is a particular realization of multiconfigurational self-consistent field and…

Chemical Physics · Physics 2023-08-31 Fábris Kossoski , Pierre-François Loos

The saddle point (SP) calculation is a grand challenge for computationally intensive energy function in computational chemistry area, where the saddle point may represent the transition state (TS). The traditional methods need to evaluate…

Machine Learning · Statistics 2022-11-08 Shuting Gu , Hongqiao Wang , Xiang Zhou

A central challenge to many fields of science and engineering involves minimizing non-convex error functions over continuous, high dimensional spaces. Gradient descent or quasi-Newton methods are almost ubiquitously used to perform such…

Machine Learning · Computer Science 2014-06-11 Yann Dauphin , Razvan Pascanu , Caglar Gulcehre , Kyunghyun Cho , Surya Ganguli , Yoshua Bengio

We combine recent advances in excited state variational principles, fast multi-Slater Jastrow methods, and selective configuration interaction to create multi-Slater Jastrow wave function approximations that are optimized for individual…

Strongly Correlated Electrons · Physics 2019-06-19 Sergio D. Pineda Flores , Eric Neuscamman

The potential of mean-field decomposition techniques in interpreting electronic transitions in molecules is explored, particularly, the usefulness of these for offering computational signatures of different classes of such excitations. When…

Chemical Physics · Physics 2022-02-14 Janus J. Eriksen

This paper focuses on the distributed optimization of stochastic saddle point problems. The first part of the paper is devoted to lower bounds for the centralized and decentralized distributed methods for smooth (strongly) convex-(strongly)…

Machine Learning · Computer Science 2025-04-28 Aleksandr Beznosikov , Valentin Samokhin , Alexander Gasnikov

A recent modification of the Perdew-Zunger self-interaction-correction (SIC) to the density-functional formalism (Pederson, Ruzsinszky, Perdew) has provided a framework for explicitly restoring unitary invariance to the expression for the…

Chemical Physics · Physics 2015-06-23 Mark R. Pederson

We develop a generalization of the Kohn-Sham density functional theory (KS-DFT) + Hubbard $U$ (DFT+$U$) method to the excited-state regime. This has the form of Hubbard $U$ corrected linear-response time-dependent DFT, or `TDDFT+$U$'.…

Strongly Correlated Electrons · Physics 2019-04-24 Okan K. Orhan , David D. O'Regan

Selective configuration interaction methods approximate correlated molecular ground- and excited states by considering only the most relevant Slater determinants in the expansion. While a recently proposed neural-network-assisted approach…

We present an efficient computational approach to perform real-space electronic structure calculations using an adaptive higher-order finite-element discretization of Kohn-Sham density-functional theory (DFT). To this end, we develop an…

Computational Physics · Physics 2015-06-05 Phani Motamarri , Michael R Nowak , Kenneth Leiter , Jaroslaw Knap , Vikram Gavini

Density functional theory is the workhorse of modern electronic structure calculations, with wide-ranging applications in chemistry, physics, materials science, and machine learning. At its heart lies the exchange-correlation functional, a…

Chemical Physics · Physics 2026-02-20 Fabien Tran , Susi Lehtola , Stefano Pittalis , Miguel A. L. Marques

Quantum algorithms require accurate representations of electronic states on a quantum device, yet the approximation of electronic wave functions for strongly correlated systems remains a profound theoretical challenge, with existing methods…

Quantum Physics · Physics 2025-04-29 Dipanjali Halder , Dibyendu Mondal , Rahul Maitra

Standard approximations for the exchange-correlation (XC) functional in Kohn-Sham density functional theory (KS-DFT) typically lead to unacceptably large errors when applied to strongly-correlated electronic systems. Partition-DFT (PDFT) is…

Chemical Physics · Physics 2023-09-12 Yi Shi , Yuming Shi , Adam Wasserman

The excitation energies and ionization potentials of the atoms in the first transition series are notoriously difficult to compute accurately. Errors in calculated excitation energies can range from 1--4 eV at the Hartree-Fock level, and…

chem-ph · Physics 2009-10-22 Thomas V. Russo , Richard L. Martin , P. Jeffrey Hay