Structure, reactions, and electronic spectra of the rare gas cyanohydrides and isocyanohydrides, HRgCN and HRgNC (Rg = Xe or Rn)

The low-energy electronic excitations of HRgCN and HRgNC (Rg = Xe, Rn) were computed at the TDDFT level of theory, both in the gas phase and in xenon cluster. It was found that the most prominent peak in the spectra was due to the highest occupied molecular orbital (HOMO) to lowest unoccupied molecu...

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Bibliographic Details
Published in:	Journal of physics. B, Atomic, molecular, and optical physics Atomic, molecular, and optical physics, 2020-12, Vol.53 (24), p.245102
Main Authors:	van Hoeve, Miriam D, Klobukowski, Mariusz
Format:	Article
Language:	eng
Subjects:	electronic excited states electronic spectra kinetic isotope effect pseudopotentials rare gas cyanohydrides rare gas isocyanohydrides
Online Access:	Get full text
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Summary:	The low-energy electronic excitations of HRgCN and HRgNC (Rg = Xe, Rn) were computed at the TDDFT level of theory, both in the gas phase and in xenon cluster. It was found that the most prominent peak in the spectra was due to the highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) transition (∼6 eV for HRgCN and ∼4.5 eV for HRgNC). Cluster confinement brought about bathochromic shifts in the spectra and better agreement with experiment for HXeCN. The effects of spin-orbit coupling (SOC) in the heavier Rn systems were investigated: for HRnCN, SOC red-shifted the HOMO-LUMO peak, while it blue-shifted the HOMO-LUMO peak for HRnNC. Geometry optimizations were carried out for the HRgCN and HRgNC systems to locate minima and transition states for dissociation and isomerization. Effects of isotopic substitution on reaction rates were predicted. A new model core potentials basis set was introduced and effectiveness of several pseudopotential basis sets was studied.
ISSN:	0953-4075 1361-6455