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Second-order Perturbation Theory with Complete and Restricted Active Space Reference Functions Applied to Oligomeric Unsaturated Hydrocarbons

Moughal Shahi, A. R.; Cramer, C. J.; Gagliardi, L.
Phys. Chem. Chem. Phys. 2009, 11, 10964 (doi:10.1039/b912607d).

Multiconfigurational second-order perturbation theory based on either a complete active space reference wave function (CASSCF/CASPT2) or a restricted active space reference wave function (RASSCF/RASPT2) has been applied to compute one-electron ionization potentials and vertical electronic energy differences of oligomers of length n formed from ethylene (n = 1-10), acetylene (n = 1-5), and phenylene (n = 1-3) subunits. The RASSCF/RASPT2 approach offers an accuracy similar to CASSCF/CASPT2 at significantly reduced computational expense (both methods show good agreement with experimental data where available). It is shown that RASPT2 increases the applicability of CASPT2-type approaches by permitting the use of larger active spaces.