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In this work, we introduce three algorithmic improvements to reduce the cost and improve the scaling of orbital space variational Monte Carlo (VMC). First, we show that by appropriately screening the one- and two-electron integrals of the…

Chemical Physics · Physics 2018-07-30 Iliya Sabzevari , Sandeep Sharma

The variational two-electron reduced density matrix (v2RDM) method is generalized for the description of total angular momentum ($J$) and projection of total angular momentum ($M_{J}$) states in atomic systems described by non-relativistic…

Chemical Physics · Physics 2022-08-05 Run R. Li , Nicholas C. Rubin , A. Eugene DePrince

Noncollinear (NC) magnetism and spin-orbit coupling (SOC) are indispensable for predictive ab initio materials simulations with pronounced relativistic effects and magnetic frustration, yet they significantly increase the cost of…

An analytic gradient approach for the computation of derivatives of parity-violating (PV) potentials with respect to displacements of the nuclei in chiral molecules is described and implemented within a quasirelativistic mean-field…

Chemical Physics · Physics 2023-12-19 Sascha A Brück , Nityananda Sahu , Konstantin Gaul , Robert Berger

We present and benchmark a quantum computing approach to calculate the two-dimensional coherent spectrum (2DCS) of high-spin models. Our approach is based on simulating their real-time dynamics in the presence of several magnetic field…

Quantum Physics · Physics 2024-07-02 Martin Mootz , Peter P. Orth , Chuankun Huang , Liang Luo , Jigang Wang , Yong-Xin Yao

We present a new implementation of the driven similarity renormalization group (DSRG) based on a density matrix renormalization group (DMRG) reference. The explicit build of high-order reduced density matrices is avoided by forming…

Chemical Physics · Physics 2025-03-04 Chenyang Li , Xiaoxue Wang , Huanchen Zhai , Wei-Hai Fang

Computing equilibrium shapes of crystals (ESC) is a challenging problem in materials science that involves minimizing an orientation-dependent (i.e., anisotropic) surface energy functional subject to a prescribed mass constraint. The highly…

Numerical Analysis · Mathematics 2023-11-07 Zeyu Zhou , Wen Huang , Wei Jiang , Zhen Zhang

Orbital-optimized density functional theory (DFT) has emerged as an alternative to time-dependent (TD) DFT capable of describing difficult excited states with significant electron density redistribution, such as charge-transfer, Rydberg,…

Chemical Physics · Physics 2025-01-22 Hanh D. M. Pham , Rustam Z. Khaliullin

We present a new efficient way to perform hybrid density functional theory (DFT) based electronic structure calculation. The new method uses an interpolative separable density fitting (ISDF) procedure to construct a set of numerical…

Computational Physics · Physics 2017-07-31 Wei Hu , Lin Lin , Chao Yang

Calculations of the lowest valence {\pi}* as well as the 3s and higher energy 3p{\sigma} Rydberg excited states of the CO2 molecule are carried out using density functionals with variational optimization of the orbitals, an approach…

Chemical Physics · Physics 2026-04-08 Darío Barreiro-Lage , Gianluca Levi , Hannes Jonssón , Thanja Lamberts

The leading terms in the large-$R$ asymptotics of the functional of the one-electron reduced density matrix for the ground-state energy of the H$_2$ molecule with the internuclear separation $R$ is derived thanks to the solution of the…

Chemical Physics · Physics 2023-03-14 Jerzy Cioslowski , Christian Schilling , Rolf Schilling

Efficiently recovering dynamic correlation in strongly correlated systems without incurring prohibitive computational costs remains a central challenge in quantum chemistry. In this Perspective, we review and benchmark methods capable of…

Chemical Physics · Physics 2026-05-22 Michał Hapka , Aleksandra Tucholska , Katarzyna Pernal

It is well-known that not only the orbital ordering but also the choice of the orbitals themselves as the basis may significantly influence the computational efficiency of density-matrix renormalization group (DMRG) calculations. In this…

Strongly Correlated Electrons · Physics 2013-06-14 Yingjin Ma , Haibo Ma

Reductions of the self-consistent mean field theory model of amphiphilic molecules in solvent can lead to a singular family of functionalized Cahn-Hilliard energies. We modify these energies, mollifying the singularities to stabilize the…

Computational Physics · Physics 2024-05-21 Andrew Christlieb , Keith Promislow , Zengqiang Tan , Sulin Wang , Brian Wetton , Steven M. Wise

A direct orbital optimization method is presented for density functional calculations of excited electronic states using either a real space grid or a plane wave basis set. The method is variational, provides atomic forces in the excited…

Computational Physics · Physics 2022-11-09 Aleksei V. Ivanov , Gianluca Levi , Elvar Ö. Jónsson , Hannes Jónsson

Density functionals at the level of the Generalized Gradient Approximation (GGA) and a plane-wave basis set are widely used today to perform ab initio molecular dynamics (AIMD) simulations. Going up in the ladder of accuracy of density…

Computational Physics · Physics 2021-10-18 Sagarmoy Mandal , Ritama Kar , Tobias Kloeffel , Bernd Meyer , Nisanth N. Nair

Calculating excited-state gradients and derivative couplings using time-dependent density functional theory (TDDFT) remains a computationally demanding task. An efficient variant, TDDFT with resolution of the identity and a minimal…

Chemical Physics · Physics 2025-11-26 Zhichen Pu , Xiaojie Wu , Yuanheng Wang , Cheng Fan , Wen Yan , Zehao Zhou , Yi Qin Gao , Qiming Sun

Understanding the process of molecular photoexcitation is crucial in various fields, including drug development, materials science, photovoltaics, and more. The electronic vertical excitation energy is a critical property, for example in…

Chemical Physics · Physics 2025-03-26 Tingting Zhao , Devin A. Matthews

Accurately modeling photochemical reactions is difficult due to the presence of conical intersections and locally avoided crossings as well as the inherently multiconfigurational character of excited states. As such, one needs a multi-state…

Chemical Physics · Physics 2024-04-26 Matthew R. Hennefarth , Matthew R. Hermes , Donald G. Truhlar , Laura Gagliardi

The density functional theory (DFT) in electronic structure calculations can be formulated as either a nonlinear eigenvalue or direct minimization problem. The most widely used approach for solving the former is the so-called…

Computational Physics · Physics 2013-08-14 Xin Zhang , Jinwei Zhu , Zaiwen Wen , Aihui Zhou