The predicted infrared spectrum of the hypermetallic molecule CaOCa in its lowest two electronic states (X)over-tilde(1)Sigma(+)(g); and (a)over-tilde(3)Sigma(+)(u)
Abstract
This study of CaOCa is our third paper in a series on Group 2 alkaline-earth M2O hypermetallic oxides. As with our previous calculations for BeOBe and MgOMg, the ab initio calculations we report here show that CaOCa has a linear 1 Sigma(+)(g) ground electronic state and a very low lying linear (a) over tilde (3)Sigma(+)(u) first excited triplet electronic state. For CaOCa we determine that the singlet-triplet splitting T-e((a) over tilde) = 386 cm(-1). We calculate the three-dimensional potential energy surface, and the electric dipole moment surfaces, of each of the two states using a multireference configuration interaction (MRCISD) approach in combination with internally contracted multireference perturbation theory (RS2C) based on full-valence complete active space self-consistent field (FV-CASSCF) wavefunctions with a cc-pwCVQZ-DK basis set for Ca and a cc-pCVQZ basis set for O. We simulate the infrared absorption spectra of Ca-40 (OCa)-O-16-Ca-40 in each of these electronic state...s in order to aid in its eventual spectroscopic characterization.
Keywords:
CaOCa / Ab initio 3D potential energy surfaces / Rovibronic spectraSource:
Journal of Molecular Structure, 2012, 1023, 101-107Publisher:
- Elsevier
Projects:
- The study of physicochemical and biochemical processes in living environment that have impacts on pollution and the investigation of possibilities for minimizing the consequences (RS-172001)
- Alexander von Humboldt Foundation (Germany)
- Marsden Fund (Wellington)
- German Academic Exchange Service (DAAD)
- International Mobility Fund (Wellington)
- Deutsche Forschungsgemeinschaft
- Fonds der Chemischen Industrie
DOI: 10.1016/j.molstruc.2012.03.048
ISSN: 0022-2860