A Systematic Comparison of Second-Order Polarization Propagator Approximation (SOPPA) and Equation-of-Motion Coupled Cluster Singles and Doubles (EOM-CCSD) Spin-Spin Coupling Constants for Selected Singly Bonded Molecules, and the Hydrides NH3, H2O, and HF and Their Protonated and Deprotonated Ions and Hydrogen-Bonded Complexes.

Abstract

Second-order polarization propagator approximation (SOPPA) and equation-of-motion coupled cluster singles and doubles (EOM-CCSD) methods have been employed for the calculation of one-bond spin-spin coupling constants in series of small molecules and ions, and of one- and two-bond coupling constants across X-H···Y hydrogen bonds. For isolated molecules, one-bond SOPPA coupling constants (1)J(X-Y) involving (13)C, (15)N, (17)O, and (19)F have larger absolute values than corresponding EOM-CCSD coupling constants, with the EOM-CCSD values being in significantly better agreement with available experimental data. The difference between SOPPA and EOM-CCSD tends to increase as the number of nonbonding electrons on the coupled atoms increases, and the SOPPA values for O-F coupling are significantly in error. Similarly, the absolute values of SOPPA one-bond coupling constants (1)J(X-H) for the hydrides NH3, H2O, and FH and their protonated and deprotonated ions are greater than EOM-CCSD values, with the largest differences occurring for F-H coupling. One- and two-bond coupling constants (1)J(X-H), (1h)J(H-Y), and (2h)J(X-Y) across X-H···Y hydrogen bonds in neutral, protonated, and deprotonated complexes formed from the hydrides are similar at SOPPA and EOM-CCSD, with the largest differences again found for (1)J(F-H) in complexes with F-H as the proton donor, and (2h)J(F-F) for (FHF)(-). The signs of (1)J(X-H), (1h)J(H-Y), and (2h)J(X-Y) are the same at both levels of theory, as is their variation across the proton-transfer coordinate in F-H···NH3. SOPPA would appear to provide a reliable and more cost-effective alternative approach for computing coupling constants across hydrogen bonds, although couplings involving F may be problematic.