Direct Scaling of Primitive Valence Force Constants:  An Alternative Approach to Scaled Quantum Mechanical Force Fields

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 102; no. 8; pp. 1412 - 1424
• Main Authors: Baker, Jon, Jarzecki, Andrzej A, Pulay, Peter
• Format: Journal Article
• Language: English
• Published: American Chemical Society 19-02-1998
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp980038m

We present an alternative approach to the derivation of scaled quantum mechanical (SQM) force fields involving the direct scaling of individual primitive valence force constants from a full set of redundant valence coordinates. Our approach is completely general and more flexible than previous SQM schemes. Optimal scaling factors for various primitive stretching, bending, and torsional force constants are derived from a training set of 30 molecules containing C, O, N, H, and Cl and used to scale force constants for a further 30 molecules. Calculated vibrational frequencies are compared with experimental values for over 1500 fundamentals. Using the hybrid three-parameter B3-LYP density functional with the split-valence 6-31G* basis set, our scaling procedure gives an average error of less than 8.5 cm-1 in the scaled frequencies. The average percentage error is under 1%.