Fixed-node diffusion Monte Carlo potential energy curve of the fluorine molecule F2 using selected configuration interaction trial wavefunctions

• DOI: 10.1063/1.4905528
• Publication Date: 2015-01-29T18:00:41Z
• Authors: Emmanuel Giner; Anthony Scemama; Michel Caffarel
• Keywords: [PHYS]Physics [physics]; Chemical Physics (physics.chem-ph); Chemical Physics; Physics - Chemical Physics; 0103 physical sciences; FOS: Physical sciences; Monte Carlo Method; 01 natural sciences; 0104 chemical sciences

The potential energy curve of the F2 molecule is calculated with Fixed-Node Diffusion Monte Carlo (FN-DMC) using Configuration Interaction (CI)-type trial wavefunctions. To keep the number of determinants reasonable and thus make FN-DMC calculations feasible in practice, the CI expansion is restricted to those determinants that contribute the most to the total energy. The selection of the determinants is made using the CIPSI approach (Configuration Interaction using a Perturbative Selection made Iteratively). The trial wavefunction used in FN-DMC is directly issued from the deterministic CI program; no Jastrow factor is used and no preliminary multi-parameter stochastic optimization of the trial wavefunction is performed. The nodes of CIPSI wavefunctions are found to reduce significantly the fixed-node error and to be systematically improved upon increasing the number of selected determinants. To reduce the non-parallelism error of the potential energy curve, a scheme based on the use of a R-dependent number of determinants is introduced. Using Dunning’s cc-pVDZ basis set, the FN-DMC energy curve of F2 is found to be of a quality similar to that obtained with full configuration interaction/cc-pVQZ.