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This paper derives and demonstrates a new, purely density-based ab initio approach for calculation of the energies and properties of many-electron systems. It is based upon the discovery of relationships that govern the "mechanics" of the…

Chemical Physics · Physics 2024-09-04 James C. Ellenbogen

Configuration-interaction-type calculations on electronic and vibrational structure are often the method of choice for the reliable approximation of many-particle wave functions and energies. The exponential scaling, however, limits their…

Computational Physics · Physics 2019-05-24 Alberto Baiardi , Christopher J. Stein , Vincenzo Barone , Markus Reiher

State-specific orbital optimized approaches are more accurate at predicting core-level spectra than traditional linear-response protocols, but their utility had been restricted on account of the risk of `variational collapse' down to the…

Computation of electronic spectra is one of the most important applications of methods capturing static electron correlation, including complete-active-space self-consistent field (CASSCF) and post-CASSCF theories. Performance of these…

Chemical Physics · Physics 2025-11-19 Reza G. Shirazi , Alexander Zech , Peter Pinski , Vladimir V. Rybkin

We present a matrix-product state (MPS)-based quadratically convergent density-matrix renormalization group self-consistent-field (DMRG-SCF) approach. Following a proposal by Werner and Knowles (JCP 82, 5053, (1985)), our DMRG-SCF algorithm…

Chemical Physics · Physics 2017-08-14 Yingjin Ma , Stefan Knecht , Sebastian Keller , Markus Reiher

Variational approaches for the calculation of vibrational wave functions and energies are a natural route to obtain highly accurate results with controllable errors. However, the unfavorable scaling and the resulting high computational cost…

Chemical Physics · Physics 2017-08-14 Alberto Baiardi , Christopher J. Stein , Vincenzo Barone , Markus Reiher

We report the development of the theory and computer program for analytical nuclear energy gradients for (extended) multi-state complete active space perturbation theory (CASPT2) with full internal contraction. The vertical shifts are also…

Chemical Physics · Physics 2017-03-20 Bess Vlaisavljevich , Toru Shiozaki

We propose an exact algorithm for computing the analytical gradient within the framework of the orbital-specific-virtual (OSV) second-order M{\o}ller-Plesset (MP2) theory in resolution-of-identity (RI) approximation. We implement the exact…

Chemical Physics · Physics 2019-12-17 Ruiyi Zhou , Qiujiang Liang , Jun Yang

We develop analytical gradients of ground- and excited-state energies with respect to system parameters including the nuclear coordinates for the hybrid quantum/classical multistate contracted variational quantum eigensolver (MC-VQE)…

Quantum Physics · Physics 2021-10-12 Robert M. Parrish , Gian-Luca R. Anselmetti , Christian Gogolin

Building on the discussion in PRA 93, 042510 (2016), we present a systematic derivation of gradient corrections to the kinetic-energy functional and the one-particle density, in particular for two-dimensional systems. We derive the leading…

Quantum Gases · Physics 2017-09-08 Martin-Isbjörn Trappe , Yink Loong Len , Hui Khoon Ng , Berthold-Georg Englert

The implementation of an efficient self-consistent field (SCF) method including both scalar relativistic effects and spin-orbit interaction in density functional theory (DFT) is presented. We make use of Gaussian-type orbitals (GTOs) and…

Chemical Physics · Physics 2024-05-03 Yannick J. Franzke , Werner M. Schosser , Fabian Pauly

Iron-sulfur clusters comprise an important functional motif of the catalytic centers of biological systems, capable of enabling important chemical transformations at ambient conditions. This remarkable capability derives from a notoriously…

We present a combination of the recently developed double incremental expansion of potential energy surfaces with the well-established adaptive density-guided approach to grid construction. This unique methodology is based on the use of an…

Chemical Physics · Physics 2020-06-24 Denis G. Artiukhin , Emil Lund Klinting , Carolin König , Ove Christiansen

As a universal quantum mechanical approach to the dynamical many-body problem, the time-dependent density functional theory (TDDFT) might be inadequate to describe crucial observables that rely on two-body evolution behavior, like the…

Computational Physics · Physics 2025-11-17 Jiong-Hang Liang , Yunfeng Xiong

The electronic structure calculations remain a major bottleneck in ab initio nonadiabatic molecular dynamics. We develop an efficient TDDFT-based FSSH implementation in the GPU4PySCF package for medium-sized molecular systems. Our approach…

Chemical Physics · Physics 2026-05-08 Cheng Fan , Zhichen Pu , Zehao Zhou , Yuanheng Wang , Yi Qin Gao , Qiming Sun

The multiscale model combining the multiconfigurational self-consistent field (MCSCF) method with the fully atomistic polarizable Fluctuating Charges (FQ) force field (J. Chem. Theory Comput. 2024, 20, 9954-9967) is here extended to the…

Chemical Physics · Physics 2025-11-14 Francesco Mazza , Marco Trinari , Chiara Sepali , Chiara Cappelli

Analytical nuclear gradients for fully internally contracted complete active space second-order perturbation theory (CASPT2) are reported. This implementation has been realized by an automated code generator that can handle spin-free…

Chemical Physics · Physics 2015-02-11 Matthew K. MacLeod , Toru Shiozaki

In this work, two approaches for simulating X-ray absorption (XA) spectra with the complete active space self-consistent field (CASSCF) linear response (LR) method are introduced. The first approach employs the well-known core-valence…

Chemical Physics · Physics 2022-03-10 Benjamin Helmich-Paris

Multicomponent methods seek to treat select nuclei, typically protons, fully quantum mechanically and equivalent to the electrons of a chemical system. In such methods, it is well known that due to the neglect of electron-proton…

Chemical Physics · Physics 2020-12-21 O. Jonathan Fajen , Kurt R. Brorsen

Dynamical Mean Field Theory (DMFT) is one of the powerful computational approaches to study electron correlation effects in solid-state materials and molecules. Its practical applicability is, however, limited by the quantity of numerical…

Strongly Correlated Electrons · Physics 2024-12-23 Jannis Ehrlich , Daniel Urban , Christian Elsässer