Physics – Chemical Physics
Scientific paper
1998-08-12
Spectrochimica Acta A 55, 713-722 (1999)
Physics
Chemical Physics
RevTeX, 22 pages; for special issue of Spectrochimica Acta A "Theoretical spectroscopy, state of the science" (eds. T. J. Lee,
Scientific paper
The quartic force field of SO$_3$ was computed fully ab initio using coupled cluster (CCSD(T)) methods and basis sets of up to $spdfgh$ quality. The effect of inner-shell correlation was taken into account. The addition of tight $d$ functions is found to be essential for accurate geometries and harmonic frequencies. The equilibrium geometry and vibrational fundamentals are reproduced to within 0.0003 \AA and (on average) 1.15 cm^{-1}, respectively. We recommend the following revised values for the harmonic frequencies: $\omega_1 = 1082.7, \omega_2 = 502.6, \omega_3 = 1415.4, \omega_4 = 534.0 cm^{-1}$. In addition, we have shown that the addition of inner polarization functions to second-row elements is highly desirable even with more approximate methods like B3LYP, and greatly improves the quality of computed geometries and harmonic frequencies of second-row compounds at negligible extra computational cost. For larger such molecules, the B3LYP/VTZ+1 level of theory should be a very good compromise between accuracy and computational cost.
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