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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 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

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 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 generalization of the variational principle that is compatible with any Hamiltonian eigenstate that can be specified uniquely by a list of properties. This variational principle appears to be compatible with a wide range of…

Chemical Physics · Physics 2020-02-07 Jacqueline A. R. Shea , Elise Gwin , Eric Neuscamman

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

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 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

Variational Monte Carlo methods have recently been applied to the calculation of excited states; however, it is still an open question what objective function is most effective. A promising approach is to optimize excited states using a…

Computational Physics · Physics 2023-12-04 William A. Wheeler , Kevin G. Kleiner , Lucas K. Wagner

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

The possibility to simulate the properties of many-body open quantum systems with a large number of degrees of freedom is the premise to the solution of several outstanding problems in quantum science and quantum information. The challenge…

Quantum Physics · Physics 2019-07-03 Alexandra Nagy , Vincenzo Savona

A variational Monte Carlo method is used to generate sets of orthogonal trial functions, Psi_T(J^pi,T), for given quantum numbers in various light p-shell nuclei. These Psi_T are then used as input to Green's function Monte Carlo…

Nuclear Theory · Physics 2008-11-26 Steven C. Pieper , R. B. Wiringa , J. Carlson

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

We present a modification to variational Monte Carlo's linear method optimization scheme that addresses a critical memory bottleneck while maintaining compatibility with both the traditional ground state variational principle and our…

Strongly Correlated Electrons · Physics 2017-02-07 Luning Zhao , Eric Neuscamman

We investigate the issue of optimization stability in variance-based state-specific variational Monte Carlo, discussing the roles of the objective function, the complexity of wave function ansatz, the amount of sampling effort, and the…

Chemical Physics · Physics 2022-12-20 Leon Otis , Eric Neuscamman

Solutions to many-body problem instances often involve an intractable number of degrees of freedom and admit no known approximations in general form. In practice, representing quantum-mechanical states of a given Hamiltonian using available…

Quantum Physics · Physics 2020-11-10 Andrey Kardashin , Alexey Uvarov , Dmitry Yudin , Jacob Biamonte

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

We review the use of continuum quantum Monte Carlo (QMC) methods for the calculation of energy gaps from first principles, and present a broad set of excited-state calculations carried out with the variational and fixed-node diffusion QMC…

Materials Science · Physics 2018-08-22 Ryan J. Hunt , Marcin Szyniszewski , Genki I. Prayogo , Ryo Maezono , Neil D. Drummond

We present a variational function that targets excited states directly based on their position in the energy spectrum, along with a Monte Carlo method for its evaluation and minimization whose cost scales polynomially for a wide class of…

Strongly Correlated Electrons · Physics 2016-01-22 Luning Zhao , Eric Neuscamman

We introduce a novel method of efficiently simulating the non-equilibrium steady state of large many-body open quantum systems with highly non-local interactions, based on a variational Monte Carlo optimization of a matrix product operator…

Quantum Physics · Physics 2024-09-18 Dawid A. Hryniuk , Marzena H. Szymańska
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