Conventional strain energies of azetidine and phosphetane: Can density functional theory yield reliable results?

The conventional strain energies for azetidine and phosphetane are determined within the isodesmic, homodesmotic, and hyperhomodesmotic models. Optimum equilibrium geometries, harmonic vibrational frequencies, and corresponding electronic energies and zero‐point vibrational energies are computed for all pertinent molecular systems using self‐consistent field theory, second‐order perturbation theory, and density functional theory and using the correlation consistent basis sets cc‐pVDZ, cc‐pVTZ, and cc‐pVQZ. Single point fourth‐order perturbation theory, CCSD, and CCSD(T) calculations using the cc‐pVTZ and the cc‐pVQZ basis sets are computed using the MP2/cc‐pVTZ and MP2/cc‐pVQZ optimized geometries, respectively, to ascertain the contribution of higher order correlation effects and to determine if the quadruple‐zeta valence basis set is needed when higher order correlation is included. In the density functional theory study, eight different functionals are used including B3LYP, wB97XD, and M06‐2X to determine if any functional can yield results similar to those obtained at the CCSD(T) level. © 2012 Wiley Periodicals, Inc. Previous attempts to calculate reliable conventional strain energies with density functional theory have met with limited success. Here, the conventional strain energies of azetidine and both conformations of phosphetane are calculated with 10 different functionals and these results are compared to MP2 and CCSD(T) values to illustrate that the right choice of functional can make the difference.