Optimal Orbital Selection for Full Configuration Interaction (OptOrbFCI): Pursuing Basis Set Limit under Budget

Full configuration interaction (FCI) solvers are limited to small basis sets due to their expensive computational costs. An optimal orbital selection for FCI (OptOrbFCI) is proposed to boost the power of existing FCI solvers to pursue the basis set limit under computational budget. The method effectively finds an optimal rotation matrix to compress the orbitals of large basis sets to one with a manageable size, conducts FCI calculations only on rotated orbital sets, and produces a variational ground-state energy and its wave function. Coupled with coordinate descent full configuration interaction (CDFCI), we demonstrate the efficiency and accuracy of the method on carbon dimer and nitrogen dimer under basis sets up to cc-pV5Z. We also benchmark the binding curve of nitrogen dimer under cc-pVQZ basis set with 28 selected orbitals, which provide consistently lower ground-state energies than the FCI results under cc-pVDZ basis set. The dissociation energy in this case is found to be of higher accuracy.