The existence of a two-center, three-electron hemibond in the first solvation shell •OH(aq) has long been matter debate. manifests ab initio molecular dynamics simulations as small-r feature oxygen radial distribution function (RDF) for H2O···•OH, but that disappears when semilocal density functionals are replaced with hybrids, suggesting self-interaction artifact. Using periodic at PBE0+D3 lev...

In this work, 242 NMR spin–spin coupling constants (SSCC) in 20 molecules are calculated, either with correlated wave function methods, SOPPA and HRPA(D), or density functional theory based on the B3LYP, BHandH, PBE0 functionals. The calculations were carried out without treatment of solvation via a polarizable continuum model both geometry optimization step and/or SSCC calculation, thereby, fo...

We study the electronic and optical properties of 39 small molecules containing transition metal atoms and 7 others related to quantum-dots for photovoltaics. We explore in particular the merits of the many-body GW formalism, as compared to the ΔSCF approach within density functional theory, in the description of the ionization energy and electronic affinity. Mean average errors of 0.2-0.3 eV w...

Predicting accurate bond length alternations (BLAs) in long conjugated oligomers has been a significant challenge for electronic-structure methods for many decades, made particularly important by the close relationships between BLA and the rich optoelectronic properties of π-delocalized systems. Here, we test the accuracy of recently developed, and increasingly popular, double hybrid (DH) funct...

The GIAO-PBE0/SARC-ZORA(Pt)∪6-31+G(d)(E) (E = main group element) computational protocol without including relativistic and spin-orbit effects is offered here for the accurate prediction of the (195)Pt NMR chemical shifts of a series of cis-(amine)2PtX2 (X = Cl, Br, I) anticancer agents (in total 42 complexes) and cis-diacetylbis(amine)platinum(II) complexes (in total 12) in solutions employing...

We present the WCCR10 data set of 10 ligand dissociation energies of large cationic transition metal complexes for the assessment of approximate exchange-correlation functionals. We analyze nine popular functionals, namely BP86, BP86-D3, B3LYP, B3LYP-D3, B97-D-D2, PBE, TPSS, PBE0, and TPSSh by mutual comparison and by comparison to experimental gas-phase data measured with well-known precision....

We investigate the performance of a set recently introduced range-separated double-hybrid functionals, namely ?B2-PLYP, ?B2GP-PLYP, RSX-0DH, and RSX-QIDH models for hard-to-calculate excitation energies. compare with parent (B2-PLYP, B2GP-PLYP, PBE0-DH, PBE-QIDH) other (DSD-PBEP86) as well some most widely employed hybrid functionals (B3LYP, PBE0, M06-2X, ?B97X). For this purpose, we select num...