The X40×10 Halogen Bonding Benchmark Revisited: Surprising Importance of (n–1)d Subvalence Correlation: Surprising Importance of (n-1)d Subvalence Correlation

Manoj K. Kesharwani, Debashree Manna, Nitai Sylvetsky, Jan M. L. Martin

Research output: Contribution to journalArticlepeer-review

Abstract

We have re-evaluated the X40×10 benchmark for halogen bonding using conventional and explicitly correlated coupled cluster methods. For the aromatic dimers at small separation, improved CCSD(T)-MP2 "high-level corrections" (HLCs) cause substantial reductions in the dissociation energy. For the bromine and iodine species, (n-1)d subvalence correlation increases dissociation energies and turns out to be more important for noncovalent interactions than is generally realized; (n-1)sp subvalence correlation is much less important. The (n-1)d subvalence term is dominated by core-valence correlation; with the smaller cc-pVDZ-F12-PP and cc-pVTZ-F12-PP basis sets, basis set convergence for the core-core contribution becomes sufficiently erratic that it may compromise results overall. The two factors conspire to generate discrepancies of up to 0.9 kcal/mol (0.16 kcal/mol RMS) between the original X40×10 data and the present revision.
Original languageEnglish
Pages (from-to)2184-2197
Number of pages14
JournalThe journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
Volume122
Issue number8
DOIs
StatePublished - 1 Mar 2018

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