Details

Autor(en) / Beteiligte

• Huber, Stefan E.
• Dalnodar, Silvia
• Kausch, Wolfgang
• Kimeswenger, Stefan
• Probst, Michael

Titel

Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule

Ist Teil von

• AIP advances, 2012-09, Vol.2 (3), p.032180-032180-15

Ort / Verlag

AIP Publishing LLC

Erscheinungsjahr

2012

Link zum Volltext

Quelle

Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals

Beschreibungen/Notizen

• 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.