Cadmium–carbon wavenumber analysis using B3LYP level theory calculations in investigations of dimethylcadmium decomposition

Computational chemistry has been widely used to understand homogeneous reactions and to support spectroscopy analysis. Thus, it is a useful tool to understand gas‐phase dynamics of metal organic chemical vapor deposition (MOCVD). In this study, we report that the basis set selection possibly results in unequivocal peak assignment in Raman spectroscopy, especially when an effective core potential (ECP) is employed. The basis set selection for the decompositionof dimethylcadmium (DMCd), for example, was examined using five different ECPs (i.e. CRENBS, CRENBL, SDD, LanL2DZ and SBKJC for Cd atom combined with STO‐3G, 3‐21G, 6‐31G(d), 6‐311G(d) and 6‐311++G(2d,2p) for C and H atoms). The analyses demonstrated that the SDD/STO‐3G/3‐21G combination for Cd/C/H atoms best reproduce the experimentally reported Cd C vibrational stretching modes of Cd(CH₃)₂ (DMCd) and •CdCH₃ (MMCd). Although the SDD/STO‐3G/3‐21G combination consists of simple and basic basis sets, we found that a good potential balance between metal (Cd) and auxiliary (C) atoms is essential to estimate frequencies suitable for spectroscopy analysis computationally. The same combination of basis set was then used to examine other possible reaction steps, and Raman experiments successfully detected one of the suggested intermediates of (CdCH₃)₂. Copyright © 2009 John Wiley & Sons, Ltd.