Physical Nature of Differential Spin-State Stabilization of Carbenes by Hydrogen and Halogen Bonding: A Domain-Based Pair Natural Orbital Coupled Cluster Study.

ABSTRACT: The variation in the singlet-triplet energy gap of diphenylcarbene (DPC) upon interaction with hydrogen (water and methanol) or halogen bond (XCF₃, X = Cl, Br, I) donors to form van der Waals (vdW) complexes is investigated in relation to the electrostatic and dispersion components of such intermolecular interactions. The domain-based local pair natural orbital coupled cluster method, DLPNO-CCSD(T), is used for calculating accurate single-triplet energy gaps and interaction energies for both spin states. The local energy decomposition scheme is used to provide an accurate quantification to the various interaction energy components at the DLPNO-CCSD(T) level. It is shown that the formation of vdW adducts stabilizes the singlet state of DPC, and in the case of water, methanol, and

SUBMITTER: Ghafarian Shirazi R 

PROVIDER: S-EPMC6727382 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature