Ab initio spectroscopy of the aluminum methylene (AlCH2) free radical

Abstract

Extensive ab initio investigations of the ground and electronic excited states of the AlCH2 free radical have been carried out in order to predict the spectroscopic properties of this, as yet, undetected species. Difficulties with erratic predictions of the ground state vibrational frequencies, both in the literature and in the present work, have been traced to serious broken-symmetry instabilities in the unrestricted Hartree-Fock orbitals at the ground state equilibrium geometry. The use of restricted open-shell Hartree–Fock or complete active space self consistent field orbitals avoids these problems and leads to consistent and realistic sets of vibrational frequencies for the ground state. Using the internally contracted multireference configuration interaction method with aug-cc-pV(T+d)Z basis sets, we have calculated the geometries, energies, dipole moments, and vibrational frequencies of eight electronic states of AlCH2 and AlCD2. In addition, we have generated Franck–Condon simulations of the expected vibronic structure of the Ã−X̃, B̃−X̃, C̃−X̃, and C̃−Ã band systems, which will be useful in searches for the electronic spectra of the radical. We have also simulated the expected rotational structure of the 0–0 absorption bands of these transitions at modest resolution under supersonic expansion cooled conditions. Our conclusion is that if AlCH2 can be generated in sufficient concentrations in the gas phase, it is most likely detectable through the B̃2A2–X̃2B1 or C̃2A1–X̃2B1 electronic transitions at 515 nm and 372 nm, respectively. Both band systems have vibrational and rotational signatures, even at modest resolution, that are diagnostic of the aluminum methylene free radical.