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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

All-electron Fixed-node Diffusion Monte Carlo (FN-DMC) calculations for the nonrelativistic ground-state energy of the water molecule at equilibrium geometry are presented. The determinantal part of the trial wavefunction is obtained from a…

Chemical Physics · Physics 2016-05-25 Michel Caffarel , Thomas Applencourt , Emmanuel Giner , Anthony Scemama

We present a variational Monte Carlo algorithm for estimating the lowest excited states of a quantum system which is a natural generalization of the estimation of ground states. The method has no free parameters and requires no explicit…

Computational Physics · Physics 2024-09-04 David Pfau , Simon Axelrod , Halvard Sutterud , Ingrid von Glehn , James S. Spencer

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

We perform excited-state variational Monte Carlo and diffusion Monte Carlo calculations using a simple and efficient wave function ansatz. This ansatz follows the recent variation-after-response formalism, accurately approximating a…

Strongly Correlated Electrons · Physics 2018-12-24 Nick S. Blunt , Eric Neuscamman

In this communication, we propose a method for obtaining isolated excited states within the Full Configuration Interaction Quantum Monte Carlo framework. This method allows for stable sampling with respect to collapse to lower energy states…

Strongly Correlated Electrons · Physics 2014-10-10 George H. Booth , Garnet Kin-Lic Chan

We recently proposed a novel approach to converging electronic energies equivalent to high-level coupled-cluster (CC) computations by combining the deterministic CC($P$;$Q$) formalism with the stochastic configuration interaction (CI) and…

Chemical Physics · Physics 2021-03-23 J. Emiliano Deustua , Jun Shen , Piotr Piecuch

The quantum Monte Carlo (QMC) is one of the most promising many-body electronic structure approaches. It employs stochastic techniques for solving the stationary Schr\" odinger equation and for evaluation of expectation values. The key…

Other Condensed Matter · Physics 2007-12-20 Michal Bajdich

Quantum Monte Carlo (QMC) methods such as Variational Monte Carlo, Diffusion Monte Carlo or Path Integral Monte Carlo are the most accurate and general methods for computing total electronic energies. We will review methods we have…

Computational Physics · Physics 2007-05-23 David Ceperley , Mark Dewing , Carlo Pierleoni

We develop a novel multi-configurational Symmetrized Projector Quantum Monte Carlo (MSPQMC) method to calculate excited state properties of Hubbard models. We compare the MSPQMC results for finite Hubbard chains with exact results (where…

Condensed Matter · Physics 2009-10-28 Bhargavi Srinivasan , S. Ramasesha , H. R. Krishnamurthy

Despite significant advances in electronic structure methods for the treatment of excited states, attaining an accurate description of the photoinduced processes in photoactive biomolecules is proving very difficult. For the prototypical…

Other Condensed Matter · Physics 2009-11-10 Friedemann Schautz , Francesco Buda , Claudia Filippi

We present a new approach to calculate excited states with the full configuration interaction quantum Monte Carlo (FCIQMC) method. The approach uses a Gram-Schmidt procedure, instantaneously applied to the stochastically evolving…

Computational Physics · Physics 2015-10-28 N. S. Blunt , Simon D. Smart , George H. Booth , Ali Alavi

A recently developed self-healing diffusion Monte Carlo algorithm [PRB 79, 195117] is extended to the calculation of excited states. The formalism is based on an excited-state fixed-node approximation and the mixed estimator of the…

Strongly Correlated Electrons · Physics 2015-05-13 Fernando A. Reboredo

Two state-of-the-art computational approaches: quantum Monte Carlo (QMC), based on accurate total energies, and GW with exciton effects (GW-BSE), based on perturbation theory are employed to calculate ionization potentials, electron…

Materials Science · Physics 2009-10-31 Jeffrey C. Grossman , Michael Rohlfing , Lubos Mitas , Steven G. Louie , Marvin L. Cohen

Diffusion Monte Carlo (DMC) based on fixed-node approximation has enjoyed significant developments in the past decades and become one of the go-to methods when accurate ground state energy of molecules and materials is needed. The remaining…

Chemical Physics · Physics 2023-08-07 Weiluo Ren , Weizhong Fu , Xiaojie Wu , Ji Chen

The essence of atomic structure theory, quantum chemistry, and computational materials science is solving the multi-electron stationary Schr\"odinger equation. The Quantum Monte Carlo-based neural network wave function method has surpassed…

Atomic Physics · Physics 2023-12-27 JinDe Liu , Chenglong Qin , Xi He , Gang Jiang

We extend Quantum Computing Quantum Monte Carlo (QCQMC) beyond ground-state energy estimation by systematically constructing the quantum circuits used for state preparation. Replacing the original Variational Quantum Eigensolver (VQE)…

We present a new method for modeling electronically excited states that overcomes a key failing of linear response theory by allowing the underlying ground state ansatz to relax in the presence of an excitation. The method is variational,…

Chemical Physics · Physics 2016-09-21 Eric Neuscamman

Obtaining accurate ground and low-lying excited states of electronic systems is crucial in a multitude of important applications. One ab initio method for solving the Schr\"odinger equation that scales favorably for large systems is…

Chemical Physics · Physics 2023-01-19 Mike Entwistle , Zeno Schätzle , Paolo A. Erdman , Jan Hermann , Frank Noé

We present in detail the recently developed multi-configurational symmetrized projector quantum Monte Carlo (MSPQMC) method for excited states of the Hubbard model. We describe the implementation of the Monte Carlo method for a…

Condensed Matter · Physics 2009-10-28 Bhargavi Srinivasan , S. Ramasesha , H. R. Krishnamurthy