Vibrational energy levels of difluorodioxirane computed with variational and perturbative methods from a hybrid force field

We have computed vibrational energy levels of difluorodioxirane (CF2O2). For the potential, a Taylor expansion in normal coordinates is used. The CCSD(T) and MP2 methods and correlation consistent basis sets of quadruple-zeta quality are used to determine the force constants. The vibrational Schrödinger equation was solved using both a variational method and second order perturbation theory. The Watson kinetic energy operator and a discrete variable representation were used with the DEWE (E. Mátyus, G. Czakó, B.T. Sutcliffe and A.G. Császár, J. Chem. Phys. 127 (2007) 084102) computer program to do the variational calculations. For the variational calculations, the average absolute deviation of fundamentals, with respect to experimental values, is less than 3 cm−1. Perturbative results are almost as good. About 300 vibrational levels were computed. 16O → 18O isotopic shifts have also been calculated variationally for the lowest 75 vibrational energy levels and are compared to experimental results.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Vibrational energy levels of difluorodioxirane (CF2O2) ► Taylor series potential in normal coordinates. ► CCSD(T) and MP2 force constants. ► Variational method