Assessment of Various Density Functionals and Basis Sets for the Calculation of Molecular Anharmonic Force Fields
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In a previous contribution (Mol. Phys. {\bf 103}, xxxx, 2005), we established the suitability of density functional theory (DFT) for the calculation of molecular anharmonic force fields. In the present work, we have assessed a wide variety of basis sets and exchange-correlation functionals for harmonic and fundamental frequencies, equilibrium and ground-state rotational constants, and thermodynamic functions beyond the RRHO (rigid rotor-harmonic oscillator) approximation. The fairly good performance of double-zeta plus polarization basis sets for frequencies results from an error compensation between basis set incompleteness and the intrinsic error of exchange-correlation functionals. Triple-zeta plus polarization basis sets are recommended, with an additional high-exponent $d$ function on second-row atoms. All conventional hybrid GGA functionals perform about equally well: high-exchange hybrid GGA and meta-GGA functionals designed for kinetics yield poor results, with the exception of of the very recently developed BMK functional which takes a middle position along with the HCTH/407 (second generation GGA) and TPSS (meta-GGA) functionals. MP2 performs similarly to these functionals but is inferior to hybrid GGAs such as B3LYP and B97-1.
Int. J. Quantum Chem., in press (special issue on vibrational spectroscopies)
Int. J. Quantum Chem., in press (special issue on vibrational spectroscopies)