Ab initio n-electron valence state perturbation theory study of the adiabatic transitions in carbonyl molecules: formaldehyde, acetaldehyde and acetone

The application of the recently developed second-order n-electron valence state perturbation theory (NEVPT2) to small carbonyl molecules (formaldehyde, acetaldehyde, and acetone) is presented. The adiabatic transition energies are computed for the singlet and triplet n->pi*, pi->pi*, and sigma->pi* states performing a full geometry optimization of the relevant states at the single state CASSCF level and taking into account the zero point energy correction in the harmonic approximation. The agreement with the known experimental values and with previously published high level calculations confirms that NEVPT2 is an efficient tool to be used for the interpretation of molecular electronic spectra. Moreover, different insight into the nature of the excited states has been obtained. Some of the transitions presented here have never been theoretically computed previously [3(pi->pi*) and 3(sigma->pi*) adiabatic transitions in acetaldehyde and acetone] or have been studied only using moderate level (single reference based) ab initio methods (all adiabatic transitions in acetaldehyde). In the present work a consistent disagreement between NEVPT2 and experiment has been found for the 3(pi->pi*) adiabatic transition in all molecules: this result is attributed to the low intensity of the transition to the first vibrational levels of the excited state. The n->pi* singlet and triplet vertical transition energies are also reported for all the molecules.