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The computationally expensive evaluation and storage of high-rank reduced density matrices (RDMs) has been the bottleneck in the calculation of dynamic correlation for multireference wave functions in large active spaces. We present a…

Chemical Physics · Physics 2020-01-08 Ankit Mahajan , Nick S. Blunt , Iliya Sabzevari , Sandeep Sharma

We present an ab-initio dynamical configuration interaction (DCI) study of free- and Mg-porphyrin. DCI is a recently developed active space theory based on the L\"owdin downfolding technique. In the active space, static correlation is…

Materials Science · Physics 2020-06-18 Marc Dvorak , Patrick Rinke

Facilitated by a rigorous partitioning of a molecular system's orbital basis into two fundamental subspaces - a reference and an expansion space, both with orbitals of unspecified occupancy - we generalize our recently introduced many-body…

Chemical Physics · Physics 2019-12-12 Janus J. Eriksen , Jürgen Gauss

Orbital optimization procedure is widely called in electronic structure simulation. To efficiently find the orbital optimization solution, we developed a new second order orbital optimization algorithm, co-iteration augmented Hessian (CIAH)…

Chemical Physics · Physics 2017-01-11 Qiming Sun

Unitary Coupled Cluster (UCC) theory is a promising variational method for electronic structure calculations, especially for strongly correlated systems and quantum computers. However, its practical application is limited by the steep…

Chemical Physics · Physics 2026-02-05 Prateek Vaish , Brenda Rubenstein

We present an accurate method for calculating hyperfine coupling constants (HFCCs) based on the complete active space second-order perturbation theory (CASPT2) with full internal contraction. The HFCCs are computed as a first-order property…

Chemical Physics · Physics 2017-03-20 Toru Shiozaki , Takeshi Yanai

Conical intersections (CIs) are pivotal in many photochemical processes. Traditional quantum chemistry methods, such as the state-average multi-configurational methods, face computational hurdles in solving the electronic Schr\"odinger…

In a previous work (arXiv:2010.02027) we showed how the full configuration interaction (FCI) ground state energy can be obtained as a functional of an arbitrary reference wavefunction by means of a gradient descent or quasi-Newton…

Chemical Physics · Physics 2020-12-10 Carlos A. Jiménez-Hoyos

We propose an efficient deterministic method to calculate the full configuration interaction (FCI) ground state energy. This method leverages the sparseness of the Lanczos basis vectors that span the Krylov subspace associated with the…

Chemical Physics · Physics 2024-01-08 Lijun Wang

The concept of machine learning configuration interaction (MLCI) [J. Chem. Theory Comput. 2018, 14, 5739], where an artificial neural network (ANN) learns on the fly to select important configurations, is further developed so that accurate…

Chemical Physics · Physics 2019-10-31 J. P. Coe

The cost of simulating quantum many-body systems - on classical or quantum hardware - scales with the number of variational parameters, so progress at fixed computational budget hinges on more parameter-efficient ans\"atze. Configuration…

Quantum Physics · Physics 2026-05-25 Hao Zhang , Matthew Otten

The accuracy of reaction energy profiles calculated with multi-configurational electronic structure methods and corrected by multi-reference perturbation theory depends crucially on consistent active orbital spaces selected along the…

Chemical Physics · Physics 2023-04-14 Moritz Bensberg , Markus Reiher

Recently developed locally scaled self-interaction correction (LSIC) is a one-electron SIC method that, when used with a ratio of kinetic energy densities (z$_\sigma$) as iso-orbital indicator, performs remarkably well for both…

Chemical Physics · Physics 2024-01-31 Rajendra R. Zope , Yoh Yamamoto , Tunna Baruah

Building upon the efficient implementation of hybrid density functionals (HDFs) for large-scale periodic systems within the framework of numerical atomic orbital bases using the localized resolution of identity (RI) technique, we have…

Computational Physics · Physics 2025-07-03 Yu Cao , Min-Ye Zhang , Peize Lin , Mohan Chen , Xinguo Ren

A linear-scaling algorithm is presented for computing the Hartree-Fock (HF) exchange matrix using concentric atomic density fitting. The algorithm utilizes the stronger distance dependence of the three-center electron repulsion integrals…

Chemical Physics · Physics 2014-10-21 David S. Hollman , Henry F. Schaefer , Edward F. Valeev

It is shown that a prechosen set of occupied/virtual valence/core atomic/fragmental orbitals can be transformed to an equivalent set of localized occupied/virtual pre-molecular orbitals (pre-LMO), which can then be taken as probes to select…

Chemical Physics · Physics 2021-05-12 Yibo Lei , Bingbing Suo , Wenjian Liu

We develop an efficient algorithm, coordinate descent FCI (CDFCI), for the electronic structure ground state calculation in the configuration interaction framework. CDFCI solves an unconstrained non-convex optimization problem, which is a…

Chemical Physics · Physics 2019-07-03 Zhe Wang , Yingzhou Li , Jianfeng Lu

We will present the numerical evaluation of the hopping and magnetic exchange integrals for a nearest-neighbor $t-J$ model of the quarter-filled $\alpha^\prime NaV_2O_5$ compound. The effective integrals are obtained from…

Strongly Correlated Electrons · Physics 2009-10-31 Nicolas Suaud , Marie-Bernadette Lepetit

Hierarchy configuration interaction (hCI) has been recently introduced as an alternative configuration interaction (CI) route combining excitation degree and seniority number, which showed to efficiently recover both dynamic and static…

Chemical Physics · Physics 2024-02-20 Fábris Kossoski , Pierre-François Loos

Neutral uranium (U I) is a very difficult atom for theoretical calculations due to a large number of valence electrons, six, strong valence-valence and valence-core correlations, high density of states, and relativistic effects.…

Atomic Physics · Physics 2020-10-14 Igor M. Savukov
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