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Quantum Monte Carlo is an efficient technique for finding the ground-state energy and related properties of small molecules. A major challenge remains in accurate determination of a molecule's geometry, i.e. the optimal location of its…

Computational Physics · Physics 2017-04-12 Jan Vrbik

Quantum Monte Carlo methods are accurate and promising many body techniques for electronic structure calculations which, in the last years, are encountering a growing interest thanks to their favorable scaling with the system size and their…

Chemical Physics · Physics 2014-02-17 Andrea Zen , Ye Luo , Sandro Sorella , Leonardo Guidoni

Atomic forces are calculated for first-row monohydrides and carbon monoxide within electronic quantum Monte Carlo (QMC). Accurate and efficient forces are achieved by using an improved method for moving variational parameters in variational…

Chemical Physics · Physics 2009-11-10 Myung Won Lee , Massimo Mella , Andrew M. Rappe

Determining the vibrational structure of a molecule is central to fundamental applications in several areas, from atmospheric science to catalysis, fuel combustion modeling, biochemical imaging, and astrochemistry. However, when significant…

Quantum Physics · Physics 2021-12-22 Nicolas P. D. Sawaya , Francesco Paesani , Daniel P. Tabor

In this article we present a caracterization of the vibrational spectrum of the H5+ molecule using the correlation function quantum Monte Carlo (CFQMC) method and a genetic algorithm study of the topology of the potential energy surface…

Molecular vibrations underpin important phenomena such as spectral properties, energy transfer, and molecular bonding. However, obtaining a detailed understanding of the vibrational structure of even small molecules is computationally…

Quantum Physics · Physics 2020-01-24 Sam McArdle , Alex Mayorov , Xiao Shan , Simon Benjamin , Xiao Yuan

The optimization of neural wave functions in variational Monte Carlo crucially relies on a robust convergence criterion. While the energy variance is theoretically a definitive measure, its practical application as a primary convergence…

Quantum Physics · Physics 2025-11-03 Huan-Chen Shi , Er-Liang Cui , Dan Zhou

Classical algorithms for predicting the equilibrium geometry of strongly correlated molecules require expensive wave function methods that become impractical already for few-atom systems. In this work, we introduce a variational quantum…

One of the primary challenges prohibiting demonstrations of practical quantum advantages for near-term devices amounts to excessive measurement overheads for estimating relevant physical quantities such as ground state energies. However,…

We present an efficient method to find minimum energy structures using energy estimates from accurate quantum Monte Carlo calculations. This method involves a stochastic process formed from the stochastic energy estimates from Monte Carlo…

Computational Physics · Physics 2015-05-18 Lucas K. Wagner , Jeffrey C. Grossman

We investigate Monte Carlo energy and variance minimization techniques for optimizing many-body wave functions. Several variants of the basic techniques are studied, including limiting the variations in the weighting factors which arise in…

Condensed Matter · Physics 2009-10-31 P. R. C. Kent , R. J. Needs , G. Rajagopal

We develop a formalism to directly evaluate the matrix of force constants within a Quantum Monte Carlo calculation. We utilize the matrix of force constants to accurately relax the positions of atoms in molecules and determine their…

Computational Physics · Physics 2020-04-06 Yu Yang Fredrik Liu , Bartholomew Andrews , Gareth J. Conduit

The energy variance optimization algorithm over a fixed ensemble of configurations in variational Monte Carlo is formally identical to a problem of fitting data: we reexamine it from a statistical maximum-likelihood point of view. We detect…

Atomic and Molecular Clusters · Physics 2009-11-07 Dario Bressanini , Gabriele Morosi , Massimo Mella

The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of Chemistry, Biology and Atmospheric Science.…

Chemical Physics · Physics 2014-07-04 Andrea Zen , Bernhardt L. Trout , Leonardo Guidoni

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

In order to find the equilibrium geometries of molecules and solids and to perform ab initio molecular dynamics, it is necessary to calculate the forces on the nuclei. We present a correlated sampling method to efficiently calculate…

Condensed Matter · Physics 2009-10-31 Claudia Filippi , C. J. Umrigar

Several methods are available to compute the anharmonicity in semi-rigid molecules. However, such methods are not routinely employed yet because of their large computational cost, especially for large molecules. The potential energy surface…

Chemical Physics · Physics 2020-10-26 Julien Lam , Saleh Abdul-Al , Abdul-Rahman Allouche

We introduce a framework for the calculation of ground and excited state energies of bosonic systems suitable for near-term quantum devices and apply it to molecular vibrational anharmonic Hamiltonians. Our method supports generic reference…

Quantum Physics · Physics 2020-06-24 Pauline J. Ollitrault , Alberto Baiardi , Markus Reiher , Ivano Tavernelli

We propose an algorithm for accurate, systematic and scalable computation of interatomic forces within the auxiliary-field Quantum Monte Carlo (AFQMC) method. The algorithm relies on the Hellman-Fenyman theorem, and incorporates Pulay…

Computational Physics · Physics 2018-05-30 Mario Motta , Shiwei Zhang

We extend correlated sampling from classical auxiliary-field quantum Monte Carlo to the quantum-classical (QC-AFQMC) framework, enabling accurate nuclear force computations crucial for geometry optimization and reaction dynamics. Stochastic…

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