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We present a general approach to converge excited state solutions to any quantum chemistry orbital optimization process, without the risk of variational collapse. The resulting Square Gradient Minimization (SGM) approach only requires…

Chemical Physics · Physics 2020-03-11 Diptarka Hait , Martin Head-Gordon

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 a discussion of recent progress in excited-state-specific quantum chemistry and quantum Monte Carlo alongside a demonstration of how a combination of methods from these two fields can offer reliably accurate excited state…

Chemical Physics · Physics 2023-02-07 Leon Otis , Eric Neuscamman

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

A novel approach to rapidly converging high-level coupled-cluster (CC) energetics in an automated fashion is proposed. The key idea is an adaptive selection of the excitation manifolds defining higher-than-two-body components of the cluster…

Chemical Physics · Physics 2023-08-25 Karthik Gururangan , Piotr Piecuch

A size-extensive, converging, black-box, ab initio coupled-cluster ($\Delta$CC) ansatz is introduced that computes the energies and wave functions of stationary states from any degenerate or nondegenerate Slater-determinant references with…

Chemical Physics · Physics 2026-05-15 So Hirata

We propose a method to create selective interactions with Dicke-Stark model by means of time-dependent perturbation theory. By choosing the proper rotating framework, we find that the time oscillating terms depend on the number of atomic…

Quantum Physics · Physics 2021-02-03 Fengchun Mu , Ya Gao , Hong-Da Yin , Gangcheng Wang

We extend ground-state density-functional theory to excited states and provide the theoretical formulation for the widely used $\Delta SCF$ method for calculating excited-state energies and densities. As the electron density alone is…

Chemical Physics · Physics 2024-03-08 Weitao Yang , Paul W. Ayers

The recent development of the density matrix renormalization group (DMRG) method in multireference quantum chemistry makes it practical to evaluate static correlation in a large active space, while dynamic correlation provides a critical…

Strongly Correlated Electrons · Physics 2020-08-20 Zhen Luo , Yingjin Ma , Xicun Wang , Haibo Ma

Consider a quantum system $\cS$ that interacts sequentially with a chain (environment) of identical probes ${\cal C} = \cP+\cP+...$, with each interaction governed by a fixed interaction time $\tau$ and operator $V$. It is known how to…

Mathematical Physics · Physics 2011-05-31 Mark D Penney

A microscopic description of nuclei is important to understand the nuclear shell-model from fundamental principles. This is difficult to achieve for more than the lightest nuclei without an effective approximation scheme. The purpose of…

Nuclear Theory · Physics 2013-08-19 Gustav R. Jansen

Quantum Monte Carlo (QMC) is a stochastic method which has been particularly successful for ground-state electronic structure calculations but mostly unexplored for the computation of excited-state energies. Here, we show that, within a…

Chemical Physics · Physics 2018-08-09 Anthony Scemama , Anouar Benali , Denis Jacquemin , Michel Caffarel , Pierre-François Loos

We present the theoretical framework, implementation, and benchmark results for a reduced-cost relativistic equation-of-motion coupled cluster singles and doubles (EOM-CCSD) method based on state-specific frozen natural spinors (SS-FNS). In…

Delta-self-consistent field theory (delta-SCF) is a conceptually simple and computationally inexpensive method for finding excited states. Using the maximum overlap method to guide optimization of the excited state, delta-SCF has been shown…

Chemical Physics · Physics 2021-04-07 Susannah Bourne Worster , Oliver Feighan , Frederick R. Manby

Traditional multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) methods are based on a single orthonormal orbital basis (OB). For atoms with complicated shell structures, a large OB is needed to saturate all the…

Atomic Physics · Physics 2015-06-12 S. Verdebout , P. Rynkun , P. Jönsson , G. Gaigalas , C. Froese Fischer , M. Godefroid

In this second part of our series on the recently proposed many-body expanded full configuration interaction (MBE-FCI) method, we introduce the concept of multideterminantal expansion references. Through theoretical arguments and numerical…

Chemical Physics · Physics 2019-09-23 Janus J. Eriksen , Jürgen Gauss

We report the first study using active-orbital-based and adaptive CC($P$;$Q$) approaches to describe excited electronic states. These CC($P$;$Q$) methodologies are applied, alongside their completely renormalized (CR) coupled-cluster (CC)…

Chemical Physics · Physics 2025-01-08 Karthik Gururangan , Jun Shen , Piotr Piecuch

We report an investigation of the structure of $^{12}$C nucleus employing a newly developed configuration-mixing method. In the three-dimensional coordinate-space representation, we generate a number of Slater determinants with various…

Nuclear Theory · Physics 2013-08-09 Y. Fukuoka , S. Shinohara , Y. Funaki , T. Nakatsukasa , K. Yabana

We employ a generalized variational principle to improve the stability, reliability, and precision of fully excited-state-specific complete active space self-consistent field theory. Compared to previous approaches that similarly seek to…

Chemical Physics · Physics 2022-09-05 Rebecca Hanscam , Eric Neuscamman

The accurate quantum chemical calculation of excited states is a challenging task, often requiring computationally demanding methods. When entire ground and excited potential energy surfaces (PESs) are desired, e.g., to predict the…

Chemical Physics · Physics 2025-03-26 Zeno Schätzle , P. Bernát Szabó , Alice Cuzzocrea , Frank Noé
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