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Title: SOPPA and CCSD vibrational corrections to NMR indirect spin-spin coupling constants of small hydrocarbons

We present zero-point vibrational corrections to the indirect nuclear spin-spin coupling constants in ethyne, ethene, cyclopropene and allene. The calculations have been carried out both at the level of the second order polarization propagator approximation (SOPPA) employing a new implementation in the DALTON program, at the density functional theory level with the B3LYP functional employing also the Dalton program and at the level of coupled cluster singles and doubles (CCSD) theory employing the implementation in the CFOUR program. Specialized coupling constant basis sets, aug-cc-pVTZ-J, have been employed in the calculations. We find that on average the SOPPA results for both the equilibrium geometry values and the zero-point vibrational corrections are in better agreement with the CCSD results than the corresponding B3LYP results. Furthermore we observed that the vibrational corrections are in the order of 5 Hz for the one-bond carbon-hydrogen couplings and about 1 Hz or smaller for the other couplings apart from the one-bond carbon-carbon coupling (11 Hz) and the two-bond carbon-hydrogen coupling (4 Hz) in ethyne. However, not for all couplings lead the inclusion of zero-point vibrational corrections to better agreement with experiment.
Authors:
;  [1]
  1. Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø (Denmark)
Publication Date:
OSTI Identifier:
22499151
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Conference Proceedings; Journal Volume: 1702; Journal Issue: 1; Conference: ICCMSE 2015: International conference of computational methods in sciences and engineering 2015, Athens (Greece), 20-23 Mar 2015; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ACETYLENE; ALLENE; APPROXIMATIONS; C CODES; CARBON; CORRECTIONS; COUPLING CONSTANTS; DENSITY FUNCTIONAL METHOD; ETHYLENE; GEOMETRY; HYDROGEN; J-J COUPLING; NUCLEAR MAGNETIC RESONANCE; POLARIZATION; PROPAGATOR; S CODES; SPIN