Quantum Monte Carlo with density matrix: potential energy curve derived properties.

In this work, we used diffusion quantum Monte Carlo with density matrix (d-DMC) and variational quantum Monte Carlo (d-VMC) to determine the potential energy curve (PEC) and obtain the spectroscopic constants of H2 molecule in the ground state, in order to evaluate the capability of these methods to provide an accurate PEC description. These quantum Monte Carlo methods build with density matrix are new approaches to conventional quantum Monte Carlo methods based on wave function formed by product of α and β determinants. To investigate the robustness of d-DMC, we performed calculations with two different basis sets and analyzed the influence of the size of these sets on results. To the best of our knowledge, this is the first study that shows the dissociation energy and rotational constant obtained from d-QMC. We found that the quality of PEC described by the d-DMC is essentially coincident with the most accurate results available in the literature, regardless of the complexity of basis set employed.