An optimized full-configuration-interaction nuclear orbital approach to a "hard-core" interaction problem: application to (3He)(N)-Cl2(B) clusters (N < or = 4).

An efficient full-configuration-interaction nuclear orbital treatment has been recently developed as a benchmark quantum-chemistry-like method to calculate ground and excited "solvent" energies and wave functions in small doped DeltaE(est) clusters (N < or = 4) [M. P. de Lara-Castells, G. Delgado-Barrio, P. Villarreal, and A. O. Mitrushchenkov, J. Chem. Phys. 125, 221101 (2006)]. Additional methodological and computational details of the implementation, which uses an iterative Jacobi-Davidson diagonalization algorithm to properly address the inherent "hard-core" He-He interaction problem, are described here. The convergence of total energies, average pair He-He interaction energies, and relevant one- and two-body properties upon increasing the angular part of the one-particle basis set (expanded in spherical harmonics) has been analyzed, considering Cl(2) as the dopant and a semiempirical model (T-shaped) He-Cl(2)(B) potential. Converged results are used to analyze global energetic and structural aspects as well as the configuration makeup of the wave functions, associated with the ground and low-lying "solvent" excited states. Our study reveals that besides the fermionic nature of (3)He atoms, key roles in determining total binding energies and wave-function structures are played by the strong repulsive core of the He-He potential as well as its very weak attractive region, the most stable arrangement somehow departing from the one of N He atoms equally spaced on equatorial "ring" around the dopant. The present results for N = 4 fermions indicates the structural "pairing" of two (3)He atoms at opposite sides on a broad "belt" around the dopant, executing a sort of asymmetric umbrella motion. This pairing is a compromise between maximizing the (3)He-(3)He and the He-dopant attractions, and suppressing at the same time the "hard-core" repulsion. Although the He-He attractive interaction is rather weak, its contribution to the total energy is found to scale as a power of three and it thus increasingly affects the pair density distributions as the cluster grows in size.