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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

In the regime where traditional approaches to electronic structure cannot afford to achieve accurate energy differences via exhaustive wave function flexibility, rigorous approaches to balancing different states' accuracies become…

Chemical Physics · Physics 2017-11-22 Paul J. Robinson , Sergio D. Pineda Flores , Eric Neuscamman

The authors present a technique using variational Monte Carlo to solve for excited states of electronic systems. The technique is based on enforcing orthogonality to lower energy states, which results in a simple variational principle for…

Chemical Physics · Physics 2021-10-15 Shivesh Pathak , Brian Busemeyer , João N. B. Rodrigues , Lucas K. Wagner

We employ quantum Monte Carlo to obtain chemically accurate vertical and adiabatic excitation energies, and equilibrium excited-state structures for the small, yet challenging, formaldehyde and thioformaldehyde molecules. A key ingredient…

Computational Physics · Physics 2019-08-02 Monika Dash , Jonas Feldt , Saverio Moroni , Anthony Scemama , Claudia Filippi

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

We extend our hybrid linear-method/accelerated-descent variational Monte Carlo optimization approach to excited states and investigate its efficacy in double excitations. In addition to showing a superior statistical efficiency when…

Chemical Physics · Physics 2022-02-24 Leon Otis , Isaac M. Craig , Eric Neuscamman

We investigate the use of different variational principles in quantum Monte Carlo, namely energy and variance minimization, prompted by the interest in the robust and accurate estimate of electronic excited states. For two prototypical,…

Chemical Physics · Physics 2021-11-19 Alice Cuzzocrea , Anthony Scemama , Wim J. Briels , Saverio Moroni , Claudia Filippi

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

Certain point defects in solids can efficiently be used as qubits for applications in quantum technology. They have spin states that are initializable, readable, robust, and can be manipulated optically. New theoretical methods are needed…

Computational Physics · Physics 2023-09-20 Kristoffer Simula , Ilja Makkonen

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 high-accuracy correlated calculations of small Si$_x$H$_y$ molecular systems both in the ground and excited states. We employ quantum Monte Carlo (QMC) together with a variety of many-body wave function approaches based on basis…

Chemical Physics · Physics 2020-10-21 Guangming Wang , Abdulgani Annaberdiyev , Lubos Mitas

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

Quantum Monte Carlo methods are first-principle approaches that approximately solve the Schr\"odinger equation stochastically. As compared to traditional quantum chemistry methods, they offer important advantages such as the ability to…

Chemical Physics · Physics 2020-02-11 Jonas Feldt , Claudia Filippi

We show that recently developed quantum Monte Carlo methods, which provide accurate vertical transition energies for single excitations, also successfully treat double excitations. We study the double excitations in medium-sized molecules,…

In this article, we report a fully ab initio variational Monte Carlo study of the linear, and periodic chain of Hydrogen atoms, a prototype system providing the simplest example of strong electronic correlation in low dimensions. In…

Strongly Correlated Electrons · Physics 2015-05-30 Lorenzo Stella , Claudio Attaccalite , Sandro Sorella , Angel Rubio

We present a variational Monte Carlo (VMC) method that works equally well for the ground and the excited states of a quantum system. The method is based on the minimization of the variance of energy, as opposed to the energy itself in…

Computational Physics · Physics 2007-05-23 Imran Khan , Bo Gao

We present a simple and efficient method to optimize within energy minimization the determinantal component of the many-body wave functions commonly used in quantum Monte Carlo calculations. The approach obtains the optimal wave function as…

Other Condensed Matter · Physics 2009-11-11 Anthony Scemama , Claudia Filippi

Variational approaches, such as variational Monte Carlo (VMC) or the variational quantum eigensolver (VQE), are powerful techniques to tackle the ground-state many-electron problem. Often, the family of variational states is not invariant…

Quantum Physics · Physics 2023-10-10 Javier Robledo Moreno , Jeffrey Cohn , Dries Sels , Mario Motta

We present simple and practical strategies to reduce the variance of Monte Carlo estimators. Our focus is on variational Monte Carlo calculations of atomic forces and pressure in electronic systems, although we show that the underlying…

Strongly Correlated Electrons · Physics 2026-03-17 David Linteau , Saverio Moroni , Giuseppe Carleo , Markus Holzmann

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
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