Premium
Conventional strain energies of azetidine and phosphetane: Can density functional theory yield reliable results?
Author(s) -
Smith Shelley A.,
Hand Karen E.,
Love Melissa L.,
Hill Glake,
Magers David H.
Publication year - 2012
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23165
Subject(s) - isodesmic reaction , density functional theory , basis set , perturbation theory (quantum mechanics) , atomic physics , valence (chemistry) , chemistry , computational chemistry , physics , quantum mechanics
Abstract 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.