Journal of Physical Chemistry A, Vol.109, No.21, 4824-4828, 2005
Semispectroscopic and quantitative structure - Property relationship estimates of the equilibrium and vibrationally averaged structure and dipole moment of 1-buten-3-yne
Systematic quantum chemical calculations have been performed to obtain precise estimates of the equilibrium and vibrationally averaged molecular structure and electric dipole moment of vinylacetylene (VA, 1-buten3-yne). Anharmonic (cubic and semi-diagonal quartic) MP2/cc-pVTZ force fields in normal coordinates were computed to account for anharmonic vibrational effects, including zero-point contributions to the rotational constants and the electric dipole moment. A simultaneous weighted least-squares structural refinement was performed, resulting in the best semi spectroscopic estimate of the re structure of VA. The refinement was based on experimentally measured ground-state rotational constants of two isotopologs of VA corrected to equilibrium values using MP2/cc-pVTZ vibration-rotation interaction constants and all-electron CCSD(T)/aug-cc-pVTZ structural constraints. The semispectroscopic r(e) structure of VA agrees excellently with the high-level CCSD(T)/aug-cc-pVTZ ab initio structure. The most dependable, CCSD(T)/cc-pVQZ//CCSD(T)/aug-cc-pVTZ equilibrium electric dipole moment of VA, in D, is mu(a) = 0.4088, mu(b) = 0.0004, and mu(c) = 0. The vibrationally corrected a-component of 0.4214 D is in excellent agreement with one of the available experimental values. The present analysis shows that mu(b) is negligible even after vibrational correction. A simple quantitative structure-property relationship (QSPR) model resulted in a highly similar estimate, 0.45 D, for the electric dipole moment of VA.