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The carbon–carbon bonds in the ground states of C₂ and C₂H₂, at their equilibrium geometries, are compared by analysing the changes in the off‐nucleus magnetic shielding tensor within the space surrounding each of these molecules. A wide range of quantum‐chemical approaches, including full‐valence CASSCF‐GIAO, CCSD(T)‐GIAO and CCSDT‐GIAO, all with the cc‐pVQZ basis set, as well as HF‐GIAO and MP2‐GIAO, with the cc‐pVQZ, cc‐pV5Z and cc‐pV6Z basis sets, show that the surroundings of the carbon–carbon bond in C₂ are more shielded than those of the carbon–carbon bond in C₂H₂. The additional shielding of the carbon–carbon bond in C₂ is found to be due to a larger paramagnetic contribution to the component of the shielding tensor which is perpendicular to the molecular axis. The analysis of the off‐nucleus shielding data indicates that the carbon–carbon bond in C₂ is “bulkier” and …