New physical insights: Formamide discharge decomposition and the role of fragments in the formation of large biomolecules.

In this work we present a time-resolved FTIR spectroscopic study on kinetics of atomic and molecular species, specifically CO, CN radical, N2, HCN and CO2 generated in a glow discharge of formamide-nitrogen-water mixture in a helium buffer gas. Radicals such as NH, CH and OH have been proven to be fundamental stones of subsequent chemical reactions having a crucial role in a prebiotic synthesis of large organic molecules. This work contains three main goals. Firstly, we present our time-resolved spectra of formamide decomposition products and discuss the mechanism of collisional excitations between specific species. Secondly, according to our time resolution, we demonstrate and explain the band shape of CO's first overtone and the energy transfer between excited nitrogen and CO, present in our spectra. Lastly, we present theoretical results for the non-LTE modelling of the spectra using bi-temperature approach and a 1D harmonic Franck-Condon approach for the multi-molecule spectra of the formamide decomposition process in the 1800-5600 cm-1 spectral range.

Theoretical rovibronic spectroscopy of the calcium monohydroxide radical (CaOH).

The rovibronic (rotation-vibration-electronic) spectrum of the calcium monohydroxide radical (CaOH) is of interest to studies of exoplanet atmospheres and ultracold molecules. Here, we theoretically investigate the Ã2Π-X̃2Σ+ band system of CaOH using high-level ab initio theory and variational nuclear motion calculations. New potential energy surfaces (PESs) are constructed for the X̃2Σ+ and Ã2Π electronic states along with Ã-X̃ transition dipole moment surfaces (DMSs). For the ground X̃2Σ+ state, a published high-level ab initio PES is empirically refined to all available experimental rovibrational energy levels up to J = 15.5, reproducing the observed term values with a root-mean-square error of 0.06 cm-1. Large-scale multireference configuration interaction calculations using quintuple-zeta quality basis sets are employed to generate the Ã2Π state PESs and Ã-X̃ DMSs. Variational calculations consider both Renner-Teller and spin-orbit coupling effects, which are essential for a correct description of the spectrum of CaOH. Computed rovibronic energy levels of the Ã2Π state, line list calculations up to J = 125.5, and an analysis of Renner-Teller splittings in the ν2 bending mode of CaOH are discussed.

Modelling the non-local thermodynamic equilibrium spectra of silylene (SiH2).

This paper sets out a robust methodology for modelling spectra of polyatomic molecules produced in reactive or dissociative environments, with vibrational populations outside local thermal equilibrium (LTE). The methodology is based on accurate, extensive ro-vibrational line lists containing transitions with high vibrational excitations and relies on the detailed ro-vibrational assignments. The developed methodology is applied to model non-LTE IR and visible spectra of silylene (SiH2) produced in a decomposition of disilane (Si2H6), a reaction of technological importance. Two approaches for non-LTE vibrational populations of the product SiH2 are introduced: a simplistic 1D approach based on the Harmonic approximation and a full 3D model incorporating accurate vibrational wavefunctions of SiH2 computed variationally with the TROVE (Theoretical ROVibrational Energy) program. We show how their non-LTE spectral signatures can be used to trace different reaction channels of molecular dissociations.