Validation of the mPW1PW Quantum chemical calculations for the vibrational study of organic molecules – re‐assignment of the isopropylamine vibrational spectra

The validity of the mPW1PW91 density functional theory (DFT) method coupled to the all‐electron basis set 6‐31G* (mPW1PW/6‐31G*) for the study of amines, using isopropylamine (iPram) as a case study, was evaluated. Validation was performed by comparing the calculated values with the corresponding experimental results obtained and/or reported in the literature. Moreover, the accuracy of that theoretical level was compared with that of other widely used theoretical levels, namely HF/6‐31G*, B3LYP/6‐31G* and MP2/6‐31G*. The effect of basis set improvement within the mPW1PW protocol was evaluated considering the widely used 6‐311G** basis set. On the whole, the results clearly show that the mPW1PW/6‐31G* calculations are a suitable tool for the prediction of the structural and vibrational features of iPram. The validation of the theoretical methodology allowed a complete revision of the vibrational assignments previously reported in the literature, being the result of several proposed re‐assignments. Copyright © 2010 John Wiley & Sons, Ltd.