Insights into the structure and stability of the carbonic acid dimer

Murillo, Juliana; David, Jorge; Restrepo, Albeiro

doi:10.1039/c003520c

Cited by 54 publications

(72 citation statements)

References 52 publications

(97 reference statements)

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“…4 in Ref. 68. However, none of these can explain the vibrational features in the low wavenumber Raman spectrum of β‐H 2 CO 3 and α‐H 2 CO 3 better than the structures depicted in Fig.…”

Section: Resultsmentioning

confidence: 81%

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Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

Mitterdorfer

Bernard

Klauser

et al. 2011

J Raman Spectroscopy

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Two different polymorphs of carbonic acid, α-and β-H 2 CO 3 , were identified and characterized using infrared spectroscopy (FT-IR) previously. Our attempts to determine the crystal structures of these two polymorphs using powder and thin-film X-ray diffraction techniques have failed so far. Here, we report the Raman spectrum of the α-polymorph, compare it with its FT-IR spectrum and present band assignments in line with our work on the β-polymorph [Angew. Chem. Int. Ed. 48 (2009) 2690-2694]. The Raman spectra also contain information in the wavenumber range ∼90-400 cm −1 , which was not accessible by FT-IR spectroscopy in the previous work. While the α-polymorph shows Raman and IR bands at similar positions over the whole accessible range, the rule of mutual exclusion is obeyed for the β-polymorph. This suggests that there is a center of inversion in the basic building block of β-H 2 CO 3 whereas there is none in α-H 2 CO 3 . Thus, as the basic motif in the crystal structure we suggest the cyclic carbonic acid dimer containing a center of inversion in case of β-H 2 CO 3 and a catemer chain or a sheet-like structure based on carbonic acid dimers not containing a center of inversion in case of α-H 2 CO 3 . This hypothesis is strengthened when comparing Raman active lattice modes at <400 cm −1 with the calculated Raman spectra for different dimers. In particular, the intense band at 192 cm −1 in β-H 2 CO 3 can be explained by the inter-dimer stretching mode of the centrosymmetric RC(OHO) 2 CR entity with R OH. The same entity can be found in gas-phase formic acid (R H) and in β-oxalic acid (R COOH) and produces an intense Raman active band at a very similar wavenumber. The absence of this band in α-H 2 CO 3 confirms that the difference to β-H 2 CO 3 is found in the local coordination environment and/or monomer conformation rather than on the long range.

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Section: Resultsmentioning

confidence: 81%

“…Murillo et al 68 have suggested a large number of different dimers, which might serve as the fundamental dimeric unit building such a catemer chain. We have selected among these some energetically rather low‐lying dimers, which are capable of producing chainlike structures and which do not show a center of inversion.…”

Section: Resultsmentioning

confidence: 99%

Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

Mitterdorfer

Bernard

Klauser

et al. 2011

J Raman Spectroscopy

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“…+ dHF + dZPE −6.05 −5.14 level of theory, the value of ZPE at the MP2/aug-cc-pVDZ level of theory has been taken based on the observation that ZPE does only depend very weakly on basis set size. 11,13 In this case, the counterpoise correction yields a significantly different result of 3.93 kcal/mol. The reason for this is probably again that for MP2 the triple-zeta basis is still too small to yield converged results.…”

Section: Stability and Energetics Of The Dimermentioning

confidence: 97%

“…the assignments of vibrational modes 9 are still thought to be well based and only the reliable prediction of infrared spectra with MP2/aug-cc-pVDZ calculations is questioned. Murillo et al 13 investigated the energetics of different dimer geometries and especially the effect of the geometry on the strength of hydrogen bonds. They found the strongest hydrogen bonds to be associated with the dimer composed of one cis-cis and one cis-trans monomer, not for the one with two cis-cis units.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2012

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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

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“…The ASCEC algorithm [29][30][31] belongs to stochastic sampling methods and has been successfully used in the treatment of very diverse systems. [30][31][32][33][34][35][36][37][38][39][40][41][42][43] The ASCEC method consists of random walks on complex energy landscapes of atomic or molecular aggregates, producing structures that are subject to a modified Metropolis acceptance test. The resultant candidate structures are then optimized by traditional gradientbased techniques.…”

Section: Introductionmentioning

confidence: 99%

Unusual solvation through both p-orbital lobes of a carbene carbon

Hadad

Jenkins

Flórez

2015

The Journal of Chemical Physics

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As a result of a configurational space search done to explain the experimental evidence of transient specific solvation of singlet fluorocarbene amide with tetrahydrofuran, we found that the most stable structures consist in a group in which each oxygen of two tetrahydrofuran molecules act as electron donor to its respective empty p-orbital lobe of the carbene carbon atom, located at each side of the carbene molecular plane. This kind of species, which to our knowledge has not been reported before, explains very well the particular experimental characteristics observed for the transient solvation of this system. We postulate that the simultaneous interaction to both p-orbital lobes seems to confer a special stability to the solvation complexes, because this situation moves away the systems from the proximity of the corresponding transition states for the ylide products. Additionally, we present an analysis of other solvation complexes and a study of the nature of the involved interactions.

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Insights into the structure and stability of the carbonic acid dimer

Cited by 54 publications

References 52 publications

Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

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

Unusual solvation through both p-orbital lobes of a carbene carbon

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