Carbonic Acid Revisited: Vibrational Spectra, Energetics and the Possibility of Detecting an Elusive Molecule

• Main Authors: Huber, Stefan E., Dalnodar, Silvia, Kausch, Wolfgang, Kimeswenger, Stefan, Probst, Michael
• Format: Text
• Language: unknown
• Published: arXiv 2012
• Subjects: Earth and Planetary Astrophysics astro-ph.EP; Chemical Physics physics.chem-ph; FOS Physical sciences; Carbonic acid
• Online Access: https://dx.doi.org/10.48550/arxiv.1205.5483; https://arxiv.org/abs/1205.5483

We calculate harmonic frequencies of the three most abundant carbonic acid conformers. For this, different model chemistries are investigated with respect to their benefits and shortcomings. Based on these results we use perturbation theory to calculate anharmonic corrections at the ωB97XD/aug-cc-pVXZ, X=D,T,Q, level of theory and compare them with recent experimental data and theoretical predictions. A discrete variable representation method is used to predict the large anharmonic contributions to the frequencies of the stretching vibrations in the hydrogen bonds in the carbonic acid dimer. Moreover, we re-investigate the energetics of the formation of the carbonic acid dimer from its constituents water and carbon dioxide using a high-level extrapolation method. We find that the ωB97XD functional performs well in estimating the fundamental frequencies of the carbonic acid conformers. Concerning the reaction energetics, the accuracy of ωB97XD is even comparable to the high-level extrapolation method. We discuss possibilities to detect carbonic acid in various natural environments such as Earth's and Martian atmospheres. : 22 pages, 2 figures, 5 tables. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. The following article appeared in AIP Advances 2, 032180 (2012) and may be found at http://link.aip.org/link/?ADV/2/032180