Basis set choice and basis set superposition error (BSSE) in periodic Hartree–Fock calculations on molecular crystals
Literature Information
Mark A. Spackman, Anthony S. Mitchell
Periodic ab initio Hartree–Fock calculations on molecular crystals using the CRYSTAL programs are increasingly common, but to date basis set choice for these calculations seems to have been dictated more by convention rather than an informed choice from numerous alternatives. This work compares the use of basis sets built on 6-21G and 6-31G molecular basis sets with one double-zeta alternative. We show that the use of unmodified DZP basis sets is not only routinely possible, but results in substantially smaller basis set superposition error in the estimation of lattice energies. Through atomic calculations we demonstrate that, in part, this can be attributed to inherent deficiencies in the 6-21G and 6-31G basis sets, namely the constraining of valence s and p exponents to be equal. The analysis also sheds some light on the frequently cited but often poorly understood numerical instabilities that occur in calculations on some molecular crystals with the 6-31G basis set.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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