화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.110, No.4, 1575-1585, 2006
Thermochemistry of the fluoroformyloxyl radical: A computational study based on coupled cluster theory
The standard enthalpy of formation of FCO2 (X B-2(2)) was determined by a computational approach based on coupled cluster theory [CCSD(T)] with energies extrapolated to the basis-set limit, with additional corrections accounting for core-valence correlation, scalar relativity, spin-orbit coupling, and zero-point vibrational motions. Utilizing a variety of independent reaction schemes, our best estimate is Delta(f)H(0)degrees(FCO2) = -86.0 +/- 0.6 kcal mol(-1) [Delta(f)H(298)degrees(FCO2) = -86.7 +/- 0.6 kcal mol(-1)], which is shown to be more accurate than previous theoretical and experimental values. The chosen computational procedure was also applied to HCO (X (2)A'), where we find excellent agreement with experiment, and to FCO (X (2)A'), where we recommend an improved value of Delta(f)H(0)degrees(FCO) = -42.1 +/- 0.5 kcal mol(-1) [Delta(f)H(298)degrees(FCO) = -42.0 +/- 0.5 kcal mol(-1)]. Further theoretical results concern the C-F bond dissociation energy, electron affinity, ionization energy, first and second excitation energies in FCO2, fluoride ion affinity of CO2, and equilibrium geometries of the molecules treated presently. For FCO (X (2)A') we propose an improved equilibrium structure: r(e)(CF) = 132.5(2) pm, r(e)(CO) = 116.7(2) pm, and theta(e)(FCO) = 127.8(2)degrees.