A systematic theoretical study of harmonic vibrational frequencies: The ammonium ion NH4+ and other simple molecules

Analytic gradient techniques have been used to predict the harmonic vibrational frequencies of HCN, H2CO, H2O, CH4 and NH4+ at several levels of molecular electronic structure theory. Basis sets of double zeta, double zeta plus polarization, and extended plus polarization quality have been used in conjunction with self‐consistent‐field and configuration interaction methods. For the four spectroscopically characterized molecules, comparison with theory is particularly appropriate because experimental harmonic frequencies are available. For the 16 vibrational frequencies thus considered, the DZ SCF level of theory yields average errors of 166 cm−1 or 8.0%. The DZ+P SCF results are of comparable accuracy, differing on the average from experiment by 176 cm−1 or 8.3%. With the extended basis set, the comparable SCF frequency errors are only slightly less. The explicit incorporation of correlation effects qualitatively improves the agreement between theoretical and experimental harmonic vibrational frequencies....

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