THE PREDICTED INFRARED SPECTRUM OF THE HYPERMETALLIC MOLECULE CaOCa IN ITS LOWEST TWO ELECTRONIC STATES $\tilde{X}\;^{1}\Sigma_{\rm g}^+$ AND $\tilde{a}\;^{3}\Sigma_{\rm u}^+$
Loading...
Date
2012
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
This study of CaOCa is the third in a series by us on Group 2
alkaline-earth M$_2$O hypermetallic oxides. As with our previous calculations
in the series, on
BeOBe and MgOMg, the {\it ab initio} calculations we report here show that
CaOCa has a linear $^{1}\Sigma_{\rm g}^+$ ground electronic state and
a very low lying linear $\tilde{a}\;^{3}\Sigma_{\rm u}^+$
first excited triplet electronic state. For CaOCa we determine that the singlet-triplet splitting
$T_{\rm e}(\tilde a)$ = 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 $^{40}$Ca$^{16}$O$^{40}$Ca in each of these electronic states
in order to aid in its eventual spectroscopic characterization.
Description
Author Institution: Institute of Chemistry, Technology and Metallurgy; University of Belgrade, Studentski trg 14-16, 11 000 Belgrade, Serbia; Centre for Theoretical Chemistry and Physics (CTCP); The New Zealand Institute for Advanced Study(NZIAS), Massey University Auckland; Private Bag 102904, North Shore City, 0745 Auckland, New Zealand; FB C -- Physikalische und; Theoretische Chemie, Bergische Universitat; D-42097 Wuppertal, Germany