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The development of quantum computing for molecular simulations is constrained by the limited number of qubits available on current Noisy Intermediate-Scale Quantum (NISQ) devices. The present work introduces the Virtual Orbital…

Quantum Physics · Physics 2025-10-27 Federico Zahariev , Mark S. Gordon

In the past decade, natural orbital functional (NOF) approximations have emerged as prominent tools for characterizing electron correlation. Despite their effectiveness, these approaches, which rely on natural orbitals and their associated…

Chemical Physics · Physics 2024-04-19 Ion Mitxelena , Mario Piris

In the present letter, it is demonstrated how full configuration interaction (FCI) results in extended basis sets may be obtained to within sub-kJ/mol accuracy by decomposing the energy in terms of many-body expansions in the virtual…

Chemical Physics · Physics 2017-09-15 Janus J. Eriksen , Filippo Lipparini , Jürgen Gauss

Quantum phase estimation (QPE) is a promising quantum algorithm for obtaining molecular ground-state energies with chemical accuracy. However, its computational cost, dominated by the Hamiltonian 1-norm $\lambda$ and the cost of the block…

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…

Atomic Physics · Physics 2013-11-25 M. Brics , D. Bauer

The exchange-correlation energy in Kohn-Sham density functional theory is expressed as a functional of the electronic density and the Kohn-Sham orbitals. An alternative to Kohn-Sham theory is to express the energy as a functional of the…

Computational Physics · Physics 2009-10-31 S. Goedecker , C. Umrigar

While CCSD(T) with spin-restricted Hartree-Fock (RHF) orbitals has long been lauded for its ability to accurately describe closed-shell interactions, the performance of CCSD(T) on open-shell species is much more erratic, especially when…

Chemical Physics · Physics 2021-07-19 Luke W. Bertels , Joonho Lee , Martin Head-Gordon

Considering the emblematic Hartree-Fock (HF) energy expression with single Slater determinant and the ortho-normal molecular orbits (MO) in it, expressed as a linear combination (LC) of atomic orbits (LCAO) basis set functions, the HF…

Chemical Physics · Physics 2019-09-04 Sandor Kristyan

Ab initio no-core configuration interaction (NCCI) calculations for the nuclear many-body problem have traditionally relied upon an antisymmetrized product (Slater determinant) basis built from harmonic oscillator orbitals. The accuracy of…

The general procedure underlying Hartree-Fock and Kohn-Sham density functional theory calculations consists in optimizing orbitals for a self-consistent solution of the Roothaan-Hall equations in an iterative process. It is often ignored…

Chemical Physics · Physics 2017-03-16 Alain C. Vaucher , Markus Reiher

We present a density matrix approach for computing global solutions of restricted open-shell Hartree-Fock theory, based on semidefinite programming (SDP), that gives upper and lower bounds on the Hartree-Fock energy of quantum systems.…

Chemical Physics · Physics 2014-04-22 Srikant Veeraraghavan , David A. Mazziotti

Ab initio calculations face the challenge of describing a complex multiscale quantum many-body system. The nuclear wave function has both strong short-range correlations and long-range contributions. Natural orbitals provide a means of…

Nuclear Theory · Physics 2017-04-11 Chrysovalantis Constantinou

The fragment molecular orbital (FMO) scheme is one of the popular fragmentation-based methods and has the potential advantage of making the circuit flat in quantum chemical calculations on quantum computers. In this study, we used a…

Quantum Physics · Physics 2024-05-28 Kenji Sugisaki , Tatsuya Nakano , Yuji Mochizuki

The route to reliable quantum nanoelectronic devices hinges on precise control of the electrostatic environment. For this reason, accurate methods for electrostatic simulations are essential in the design process. The most widespread…

Mesoscale and Nanoscale Physics · Physics 2023-02-28 Waldemar Svejstrup , Andrea Maiani , Kevin Van Hoogdalem , Karsten Flensberg

We propose a state-averaged orbital optimization scheme for improving the accuracy of excited states of the electronic structure Hamiltonian for use on near-term quantum computers. Instead of parameterizing the orbital rotation operator in…

Chemical Physics · Physics 2024-04-09 Joel Bierman , Yingzhou Li , Jianfeng Lu

We present a natural orbital-based implementation of the intermediate Hamiltonian Fock space coupled-cluster method for (1,1) sector of Fock space. The use of natural orbital significantly reduces the computational cost and can…

Chemical Physics · Physics 2021-09-07 Soumi Haldar , Achintya Kumar Dutta

A recently developed finite element approach for fully numerical atomic structure calculations [S. Lehtola, Int. J. Quantum Chem. 119, e25945 (2019)] is extended to the description of atoms with spherically symmetric densities via…

Computational Physics · Physics 2020-01-30 Susi Lehtola

We present a reduced-cost equation-of-motion coupled-cluster method for excited states, built on a new state-specific frozen natural orbital (SS-FNO) framework. This approach enables systematic and controllable truncation of the virtual…

Chemical Physics · Physics 2025-07-24 Amrita Manna , Achintya Kumar Dutta

The Hartree-Fock-Rothaan equations are solved for He-like ions using the iterative self-consistent method. New complete and orthonormal sets of exponential-type orbitals are employed as the basis. These orbitals satisfy the orthonormality…

Quantum Physics · Physics 2025-06-26 A. Bagci , P. E. Hoggan

We have developed a reduced-cost non-Dyson third-order algebraic diagrammatic construction theory for the electron-attachment problem based on state-specific frozen natural orbitals. Density fitting and truncated natural auxiliary functions…

Chemical Physics · Physics 2026-03-13 Tamoghna Mukhopadhyay , Kamal Majee , Achintya Kumar Dutta