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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

We introduce several improvements to the penalty-based variational quantum Monte Carlo (VMC) algorithm for computing electronic excited states of Entwistle $\textit{et al.}$ [M. T. Entwistle $\textit{et al.}$, Nat. Commun. $\textbf{14}$,…

Chemical Physics · Physics 2024-09-23 P. Bernát Szabó , Zeno Schätzle , Mike T. Entwistle , Frank Noé

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

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

A quantum Monte Carlo method is introduced to optimize excited state trial wavefunctions. The method is applied in a correlation function Monte Carlo calculation to compute ground and excited state energies of bosonic van der Waals clusters…

Computational Physics · Physics 2009-11-06 M. P. Nightingale , Vilen Melik-Alaverdian

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

We present a systematically-improvable approach to core excitations in variational Monte Carlo. Building on recent work in excited-state-specific Monte Carlo, we show how a straightforward protocol, starting from a quantum chemistry guess,…

Chemical Physics · Physics 2020-10-28 Scott M. Garner , Eric Neuscamman

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

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 demonstrate that a broad class of excited state variational principles is not size consistent. In light of this difficulty, we develop and test an approach to excited state optimization that transforms between variational principles in…

Chemical Physics · Physics 2017-09-01 Jacqueline A. R. Shea , Eric Neuscamman

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 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 examine applicability of the valence bond basis correlator product state ansatz, equivalent to the restricted Boltzmann machine quantum artificial neural network ansatz, and variational Monte Carlo method for direct optimization of…

Strongly Correlated Electrons · Physics 2020-08-12 Tanja Duric , Tomislav Seva

A method is introduced to optimize excited state trial wave functions. The method is applied to ground and vibrationally excited states of bosonic van der Waals clusters of upto seven particles. Employing optimized trial wavefunctions with…

Chemical Physics · Physics 2007-05-23 M. P. Nightingale , Vilen Melik-Alaverdian

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

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

Quantum Monte Carlo (QMC) methods have proven to be highly accurate for computing excited states, but the choice of optimization strategies for multiple states remains an active topic of investigation. In this work, we revisit the…

Computational Physics · Physics 2025-04-15 Stuart Shepard , Anthony Scemama , Saverio Moroni , Claudia Filippi

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
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