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ab initio calculations; equilibrium structure; fundamentals; anharmonic force fields; spectroscopic constants; energetics
Abstract:
Highly correlated ab initio calculations with large basis sets are reported for difluorovinylidene, F2CC. Based on CCSD(T)/aug-cc-pVQZ results and taking core correlation effects properly into account, a reliable theoretical equilibrium geometry is derived: re(CC) = 134.74(10) pm, re(CF) = 131.00(10) pm, and ∠e(FCC) = 123.23(10)°. The error bars are estimated from analogous comparative calculations on the equilibrium structures of the CF2, C2, and C3 species. Correlated harmonic [CCSD(T)/aug-cc-pVQZ] and anharmonic [CCSD(T)/TZ2Pf] force fields provide theoretical values for the fundamental vibrational wavenumbers which are in excellent agreement with those measured previously in an argon matrix. Many spectroscopic constants of F2CC are predicted. In addition, the energy of F2CC relative to difluoroethyne (FCCF) and the barrier to isomerization from F2CC to FCCF have been reinvestigated by means of the present high-level ab initio calculations.
