Exoplanets & Exomoons

High-throughput Quantum Chemistry: Empowering The Search For Molecular Candidates Behind Unknown Spectral Signatures In Exoplanetary Atmospheres

By Keith Cowing
Status Report
June 21, 2023
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High-throughput Quantum Chemistry: Empowering The Search For Molecular Candidates Behind Unknown Spectral Signatures In Exoplanetary Atmospheres
Top: Predicted fundamental frequency distribution for all molecules in the CHNOPS2743-HARMONIC dataset of potential biosignatures. Please note that this plot is not a spectrum but a histogram of the all calculated frequencies. Bottom-left: Distribution of calculated vibrational transition intensities. Bottom-right: Comparison between the strongest vibrational transition intensity per molecule with its corresponding predicted fundamental frequency. Note that only intensities with up to 500 km/mol and frequencies above 2000 cm−1 are consider for the sake of readability. — astro-ph.EP

The identification of molecules in exoplanetary atmospheres is only possible thanks to the availability of high-resolution molecular spectroscopic data. However, due to its intensive and time-consuming generation process, at present, only on order 100 molecules have high-resolution spectroscopic data available, limiting new molecular detections.

Using routine quantum chemistry calculations (i.e., scaled harmonic frequency calculations using the B97-1/def2-TZVPD model chemistry with median errors of 10cm-1), here we present a complementary high-throughput approach to rapidly generate approximate vibrational spectral data for 2743 molecules made from the biologically most important elements C, H, N, O, P and S. Though these data are not accurate enough to enable definitive molecular detections and does not seek to replace the need for high-resolution data, it has powerful applications in identifying potential molecular candidates responsible for unknown spectral features.

We explore this application for the 4.1 micron (2439cm-1) feature in the atmospheric spectrum of WASP-39b, listing potential alternative molecular species responsible for this spectral line, together with SO2. Further applications of this big data compilation also include identifying molecules with strong absorption features that are likely detectable at quite low abundances, and training set for machine learning predictions of vibrational frequencies.

Characterising exoplanetary atmospheres through molecular spectroscopy is essential to understand the planet’s physico-chemical processes and likelihood of hosting life. Our rapidly generated quantum chemistry big data set will play a crucial role in supporting this understanding by giving directions into possible initial identifications of the more unusual molecules to emerge.

Juan C. Zapata Trujillo, Maria M. Pettyjohn, Laura K. McKemmish

Subjects: Earth and Planetary Astrophysics (astro-ph.EP); Chemical Physics (physics.chem-ph)
Cite as: arXiv:2306.11988 [astro-ph.EP] (or arXiv:2306.11988v1 [astro-ph.EP] for this version)
Submission history
From: Juan Camilo Zapata Trujillo
[v1] Wed, 21 Jun 2023 02:48:52 UTC (4,949 KB)
Astrobiology, Astrochemistry

Explorers Club Fellow, ex-NASA Space Station Payload manager/space biologist, Away Teams, Journalist, Lapsed climber, Synaesthete, Na’Vi-Jedi-Freman-Buddhist-mix, ASL, Devon Island and Everest Base Camp veteran, (he/him) 🖖🏻