Benchmark all-electron ab initio quantum Monte Carlo calculations for small molecules

摘要

We study the efficiency, precision and accuracy of all-electron variational and diffusion quantum Monte Carlo calculations using Slater basis sets. Starting from wave functions generated by Hartree–Fock and density functional theory, we describe an algorithm to enforce the electron-nucleus cusp condition by linear projection. For the 55 molecules in the G2 set, the diffusion quantum Monte Carlo calculations recovers an average of 95% of the correlation energy and reproduces bond energies to a mean absolute deviation of 3.2 kcal/mol. Comparing the individual total energies with essentially exact values, we investigate the error cancellation in atomization and chemical reaction path energies, giving additional insight into the sizes of nodal surface errors. © 2010 American Institute of Physics Article Outline INTRODUCTION SLATER-TYPE ORBITALS CUSP CONSTRAINT ATOMIC TOTAL ENERGIES THE G2 SET OF MOLECULES ERROR CANCELLATION CONCLUSIONS