Optimization of quantum Monte Carlo wave functions using analytical energy derivatives
Abstract
An algorithm is proposed to optimize quantum Monte Carlo (QMC) wave functions based on Newton's method and analytical computation of the first and second derivatives of the variational energy. This direct application of the variational principle yields significantly lower energy than variance minimization methods when applied to the same trial wave function. Quadratic convergence to the local minimum of the variational parameters is achieved. A general theorem is presented, which substantially simplifies the analytic expressions of derivatives in the case of wave function optimization. To demonstrate the method, the groundstate energies of the firstrow elements are calculated.
 Publication:

Journal of Chemical Physics
 Pub Date:
 February 2000
 DOI:
 10.1063/1.480839
 arXiv:
 arXiv:physics/9911005
 Bibcode:
 2000JChPh.112.2650L
 Keywords:

 31.15.Pf;
 02.30.Wd;
 02.60.Pn;
 02.50.Ng;
 Variational techniques;
 Numerical optimization;
 Distribution theory and Monte Carlo studies;
 Physics  Chemical Physics
 EPrint:
 8 pages, 3 figures