Accurate ab initio-based double many-body expansion potential energy surface for the adiabatic ground-state of the C-3 radical including combined Jahn-Teller plus pseudo-Jahn-Teller interactions

作者：Rocha C M R; Varandas A J C^*

来源：Journal of Chemical Physics, 2015, 143(7): 074302.

DOI：10.1063/1.4928434

A fully ab initio-based potential energy surface is first reported for the ground electronic state of the C3 radical using the double many-body expansion (DMBE) method. The DMBE form so obtained mimics the full set of energies calculated at the multireference configuration interaction level of theory with chemical accuracy. To account for the incompleteness of the one-and N-electron bases, the calculated external correlation energies have been scaled prior to the fitting procedure via DMBE-scaled external correlation method. Furthermore, the novel potential energy surface reproduces accurately dissociation energies, diatomic potentials, long-range interactions at all asymptotic channels, and the correct topological behavior at the region of 4 conical intersections with the partner state of the same symmetry near equilateral triangular geometries due to combined Jahn-Teller (E' circle times e') plus pseudo-Jahn-Teller [(E' + A'(1)) circle times e'] interactions. Rovibrational calculations have also been performed, unveiling a good match of the vibrational spectrum of C-3 for 53 calculated levels. The present DMBE form is, therefore, commended for both spectroscopic and reaction dynamics studies, some also performed in the present work.

• 出版日期2015-8-21