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Molecular Physics

Force calculation of polyatomic molecules in quantum Monte Carlo using Pulay's corrections

Myung Won Lee, Sergey V. Levchenko, Andrew M. Rappe

Published Oct 10, 2007• 4 citations
Publisher

Abstract

We calculated the variational and diffusion quantum Monte Carlo forces using the Hellmann–Feynman theorem and Pulay's correction for the first-row diatomic and triatomic molecules (CO, NO, CO2 and NO2). It is demonstrated that Pulay's correction is important for accurate calculation of forces on non-hydrogen atoms.
DOI
10.1080/00268970701537947

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In order to overcome the difficulty of optimizing molecular geometry using quantum Monte Carlo methods, we introduce various approximations to the exact force expectation value. We follow Pulay’s suggestion [Mol. Phys. 17, 153 (1969)] to correct the Hellmann–Feynman estimator by introducing the contributions due to the changes in the wave function with respect to the nuclear positions. When used in conjunction with energy-optimized explicitly correlated trial wave functions for H2 and LiH, these approximations appear to yield accurate forces using both the variational and diffusion Monte Carlo methods. Also, the accuracy of the second-order estimate of the Hellmann–Feynman force estimator was investigated employing our energy-optimized trial wave functions, and an erratic behavior was uncovered for some of the studied bond lengths. The additional computational cost required to compute the corrections to the Hellmann–Feynman estimator was found to be only a small fraction of the cost for a simple mean energy calculation. The same approach could be exploited also in computing the derivative of other energy-dependent quantum-mechanical observables.
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 Hellmann-Feynman theorem and incorporates Pulay corrections in the presence of atomic orbital basis sets. We benchmark the method for small molecules by comparing the computed forces with the derivatives of the AFQMC potential energy surface and by direct comparison with other quantum chemistry methods. We then perform geometry optimizations using the steepest descent algorithm in larger molecules. With realistic basis sets, we obtain equilibrium geometries in agreement, within statistical error bars, with experimental values. The increase in computational cost for computing forces in this approach is only a small prefactor over that of calculating the total energy. This paves the way for a general and efficient approach for geometry optimization and molecular dynamics within AFQMC.
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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 ideas apply more broadly to other observables, like pair-correlation and angular-distribution functions, and other methods, including molecular dynamics. For Pulay-type contributions, we show that a minor modification based on the Metropolis acceptance ratio softens the power-law divergence of the variance to a logarithmic one, and that inexpensive regularizations can further suppress outliers at the price of a controlled small bias. For Hellmann-Feynman forces, we derive compact variance-reduced estimators for periodic systems that are straightforward to implement in standard Monte Carlo codes. The approach is illustrated for high-pressure metallic hydrogen with more than a hundred atoms described by neural quantum states, including an application to molecular dynamics driven by the improved forces.
First-order derivatives of energies with respect to atomic coordinates are widely computed and used in quantum chemistry simulations. The rapidly emerging technology of quantum computing offers a new paradigm for solving relevant quantum chemistry equations. In this work, we have achieved analytical calculations of atomic forces based on the Hellmann-Feynman theorem within the framework of the variational quantum eigensolver. The accuracy of the approach is demonstrated by calculating the atomic forces of H2, LiH, H2O, and NH3 molecules, which are in excellent agreement with values obtained from full configuration interaction calculations. In particular, for systems with degenerate molecular orbitals, the analytical approach has a significant accuracy advantage over finite-difference-based methods and will not involve additional computational effort on a quantum computer. The calculated forces are further used to optimize the geometries of NH3 and CH4 molecules and to perform ab initio molecular dynamics simulations for the umbrella inversion of NH3, demonstrating the feasibility of the approach in practical quantum chemistry simulations.