Journal of Physical Chemistry A, Vol.102, No.14, 2483-2492, 1998
Ab initio calibration study of the heat of formation, geometry, and anharmonic force field of fluoroacetylene
The heat of formation, geometry, harmonic frequencies, and quartic force field of the fluoroacetylene (FCCH) molecule have been computed using coupled cluster methods and large basis sets. Inner-shell correlation was included explicitly, as were both cubic and quartic resonances, Our final force field, which does not involve any empirical adjustment, reproduces 36 vibrational band origins with a mean absolute error of 1.6 cm(-1). The bending anharmonicities exhibit a marked basis set sensitivity, due almost entirely to the CCF bend. Evidence was found for the existence of an additional quartic resonance, v(2) approximate to v(3) 2v(4). OUT best estimates, with conservative uncertainties, for the heat of formation and the geometry are 25.3 +/- 0.3 kcal/mol and r(e)(CF) = 1.2768 +/- 0.0005, r(e)(CC) = 1.1964 +/- 0.0005, and r(e)(CH) = 1.0601 +/- 0.0005 Angstrom.
Keywords:GAUSSIAN-BASIS SETS;ROTATION-VIBRATION SPECTRA;TOTAL ATOMIZATION ENERGIES;CORRELATED MOLECULAR CALCULATIONS;CONSISTENT BASIS-SETS;WAVE-FUNCTIONS;ALGEBRAIC APPROACH;VIBRON MODEL;TRIPLE EXCITATIONS;OVERTONE SPECTRA