10.6084/m9.figshare.3833520.v1
Laura K. McKemmish
Sergei N. Yurchenko
Jonathan Tennyson
<i>Ab initio</i> calculations to support accurate modelling of the rovibronic spectroscopy calculations of vanadium monoxide (VO)
2016
Taylor & Francis Group
Ab initio
spectroscopy
MRCI
transition metal diatomic
VO
2016-09-16 05:20:15
article
https://tandf.figshare.com/articles/_i_Ab_initio_i_calculations_to_support_accurate_modelling_of_the_rovibronic_spectroscopy_calculations_of_vanadium_monoxide_VO_/3833520
<p>Accurate knowledge of the rovibronic near-infrared and visible spectra of vanadium monoxide (VO) is very important for studies of cool stellar and hot planetary atmospheres. Here, the required <i>ab initio</i> dipole moment and spin-orbit coupling curves for VO are produced. This data forms the basis of a new VO line list considering 13 different electronic states and containing over 277 million transitions. Open shell transition, metal diatomics are challenging species to model through <i>ab initio</i> quantum mechanics due to the large number of low-lying electronic states, significant spinâ€“orbit coupling and strong static and dynamic electron correlation. Multi-reference configuration interaction methodologies using orbitals from a complete active space self-consistent-field (CASSCF) calculation are the standard technique for these systems. We use different state-specific or minimal-state CASSCF orbitals for each electronic state to maximise the calculation accuracy. The off-diagonal dipole moment controls the intensity of electronic transitions. We test finite-field off-diagonal dipole moments, but found that (1) the accuracy of the excitation energies were not sufficient to allow accurate dipole moments to be evaluated and (2) computer time requirements for perpendicular transitions were prohibitive. The best off-diagonal dipole moments are calculated using wavefunctions with different CASSCF orbitals.</p> <p></p>