High-resolution direct absorption infrared spectra of metastable cis-formic acid (HCOOH) trapped in a cis-well resonance behind a 15 kcal/mol barrier are reported for the first time, with the energetically unstable conformer produced in a supersonic slit plasma expansion of trans-formic acid/H 2 mixtures. We present a detailed high-resolution rovibrational analysis for cis-formic acid species in the OH stretch ( ν 1 ) fundamental, providing first precision vibrational band origin, rotational constants, and term values, which in conjunction with ab initio calculations at the couple-cluster with single, double, and perturbative triple [CCSD(T)]/ANOn (n = 0, 1, 2) level support the experimental assignments and establish critical points on the potential energy surface for internal rotor trans-to-cis isomerization. Relative intensities for a- and b-type transitions observed in the spectra permit the transition dipole moment components to be determined in the body fixed frame and prove to be in good agreement with ab initio CCSD(T) theoretical estimates but in poor agreement with simple bond-dipole predictions. The observed signal dependence on H 2 in the discharge suggests the presence of a novel H atom radical chemical mechanism for strongly endothermic “up-hill” internal rotor isomerization between trans- and cis-formic acid conformers.
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A Large-scale Approach to Modeling Molecular Biosignatures: The Diatomics
Abstract This work presents the first steps to modeling synthetic rovibrational spectra for all molecules of astrophysical interest using a new approach implemented in the Prometheus code. The goal is to create a new comprehensive source of first-principles molecular spectra, thus bridging the gap for missing data to help drive future high-resolution studies. Our primary application domain is for molecules identified as signatures of life in planetary atmospheres (biosignatures), but our approach is general and can be applied to other systems. In this work we evaluate the accuracy of our method by studying four diatomic molecules, H 2 , O 2 , N 2 , and CO, all of which have well-known spectra. Prometheus uses the transition-optimised shifted Hermite (TOSH) theory to account for anharmonicity for the fundamental ν = 0 → ν = 1 band, along with thermal-profile modeling for the rotational transitions. To this end, we expand TOSH theory to enable the modeling of rotational constants. We show that our simple model achieves results that are a better approximation of the real spectra than those produced through an harmonic approach. We compare our results with high-resolution HITRAN and ExoMol spectral data. We find that modeling accuracy tends to diminish for rovibrational transition away from the band origin, thus highlighting the need for the theory to be further adapted.
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- Award ID(s):
- 1927130
- NSF-PAR ID:
- 10358255
- Date Published:
- Journal Name:
- The Astrophysical Journal
- Volume:
- 925
- Issue:
- 1
- ISSN:
- 0004-637X
- Page Range / eLocation ID:
- 57
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3847/1538-4357/ac3976
