Experimental and ab Initio Equilibrium Structure and Harmonic Force Field of 1,2,5-Oxadiazole

Abstract

The equilibrium structure of 1,2,5-oxadiazole has been calculated ab initio at the CCSD(T) level using a polarized valence quadruple ζ basis set. The harmonic force field has also been calculated at the MP2/cc-pVTZ, B3LYP/6-311++G(3df, 2pd), and B3LYP/cc-pVQZ levels. These force fields have been subsequently scaled and further refined by fitting them to the experimental values of the vibrational fundamentals of three isotopomers and the centrifugal distortion constants of the parent molecule. The specific refinement of those scaled force constants particularly sensitive to the experimental data set was decisive for obtaining a more reliable harmonic potential. The resulting force fields are presented and used, together with the ground state rotational constants, to calculate an rz structure. The experimental r0, rs, and rm structures have also been determined. The different results have been compared and it is concluded that the ab initio structure is a good approximation of the equilibrium structure. It is also shown that the magnetic correction is not negligible, particularly for the inertial defect. Another interesting conclusion is that the anharmonicity of the C–H stretching might be unusually small.