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Zero-Variance Zero-Bias Principle for Observables in quantum Monte Carlo: Application to Forces

机译:量子蒙特卡洛中可观测物的零方差零偏差原理:对力的应用

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摘要

A simple and stable method for computing accurate expectation values of observable with Variational Monte Carlo (VMC) or Diffusion Monte Carlo (DMC) algorithms is presented. The basic idea consists in replacing the usual ``bare'' estimator associated with the observable by an improved or ``renormalized'' estimator. Using this estimator more accurate averages are obtained: Not only the statistical fluctuations are reduced but also the systematic error (bias) associated with the approximate VMC or (fixed-node) DMC probability densities. It is shown that improved estimators obey a Zero-Variance Zero-Bias (ZVZB) property similar to the usual Zero-Variance Zero-Bias property of the energy with the local energy as improved estimator. Using this property improved estimators can be optimized and the resulting accuracy on expectation values may reach the remarkable accuracy obtained for total energies. As an important example, we present the application of our formalism to the computation of forces in molecular systems. Calculations of the entire force curve of the H$_2$,LiH, and Li$_2$ molecules are presented. Spectroscopic constants $R_e$ (equilibrium distance) and $\omega_e$ (harmonic frequency) are also computed. The equilibrium distances are obtained with a relative error smaller than 1%, while the harmonic frequencies are computed with an error of about 10%.
机译:提出了一种简单稳定的方法,可通过变分蒙特卡罗(VMC)或扩散蒙特卡洛(DMC)算法计算可观测的准确期望值。基本思想在于用改进的或``重新归一化的''估计量替换与可观察到的通常的``裸''估计量。使用该估计器,可以获得更准确的平均值:不仅可以减少统计波动,而且可以减少与近似VMC或(固定节点)DMC概率密度相关的系统误差(偏差)。结果表明,改进的估计量服从零方差零偏差(ZVZB)属性,类似于使用局部能量作为改进估计量的能量的常规零方差零偏差属性。利用该特性,可以优化改进的估计量,并且期望值的最终精度可能达到针对总能量获得的显着精度。作为一个重要的例子,我们介绍了形式主义在分子系统中力的计算中的应用。给出了H $ _2 $,LiH和Li $ _2 $分子的整个力曲线的计算。还计算了光谱常数$ R_e $(平衡距离)和$ \ omega_e $(谐波频率)。获得的平衡距离的相对误差小于1%,而谐波频率的计算误差约为10%。

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  • 作者

    Assaraf, R;

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  • 年度 2003
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  • 原文格式 PDF
  • 正文语种 eng
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