The Raman and IR spectra of HCOOH and DCOOD crystals at low temperatures

Zelsmann, H.R.; Maréchal, Yves; Chosson, A.; Faure, Pierre

doi:10.1016/0022-2860(75)85043-5

Cited by 27 publications

(19 citation statements)

References 13 publications

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“…The lowering of the potential barrier found for the DPT of model hydrogen bonded systems with zero-point vibrational deformations of interacting molecules might be even more distinct in the case of complementary bases. In agreement with recent experimental evidence [26][27][28], the significant symmetrization as well as the shortening of the barrier width should favor the double proton transfer. On the other hand, the proton transfer probability may be markedly enhanced when a dynamic potential barrier is assumed [29].…”

Section: General Conclusionsupporting

confidence: 85%

Potential energy curves in complementary base pairs and in model hydrogen bonded systems

Chojnacki¹,

Lipiński²,

Sokalski³

1981

Int J of Quantum Chemistry

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The potential energy curves for the intermolecular proton transfer in complementary base pairs and respective hydrogen bonded model systems have been studied at the semiempirical all-valence and ab inirio STO-3G level. The proton transfer probability was found to be markedly greater in excited electronic states than that of the ground state. Substantial lowering of the potential barrier height for the coupled double proton transfer in model (HCOOH)2 system has been obsehed when the dynamics of zero-point vibrational deformations of the heavy atom skeleton and the environmental effects were taken into account in nonempirical STO-3G calculations. The results of quantum-chemical calculations indicate on the possibility of the double proton transfer in complementary base pairs corroborating the submolecular Lowdin hypothesis on the mechanism of spontaneous mutations.

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Section: General Conclusionsupporting

confidence: 85%

Potential energy curves in complementary base pairs and in model hydrogen bonded systems

Chojnacki¹,

Lipiński²,

Sokalski³

1981

Int J of Quantum Chemistry

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“…Milligan & Jacox (1971) previously identified DCOOD at 1726 cm −1 after vacuum-ultraviolet photolysis of D 2 O in a CO matrix at 14 K. Tso & Lee (1984) observed IR absorption frequencies of DCOOD molecules isolated in a neon matrix also at 1726 cm −1 . Two weak, broad absorptions at around 1395 and 1333 cm −1 are in fair agreement with the 2ν 5 (OD bending) and 2ν 7 (OCO deformation) bands observed at 1419 and 1327 cm −1 for polycrystalline DCOOD at 6 K (Zelsmann et al 1975). However, it should be noted that these bands were not observed in several other infrared studies of pure DCOOD ice (Millikan & Pitzer 1958) and matrix isolated DCOOD (Milligan & Jacox 1971;Tso & Lee 1984).…”

Section: Infrared Band Assignmentsupporting

confidence: 83%

Laboratory Studies on the Formation of Formic Acid (Hcooh) in Interstellar and Cometary Ices

Bennett

Hama

Kim

et al. 2010

ApJ

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Mixtures of water (H 2 O) and carbon monoxide (CO) ices were irradiated at 10 K with energetic electrons to simulate the energy transfer processes that occur in the track of galactic cosmic-ray particles penetrating interstellar ices. We identified formic acid (HCOOH) through new absorption bands in the infrared spectra at 1690 and 1224 cm −1 (5.92 and 8.17 μm, respectively). During the subsequent warm-up of the irradiated samples, formic acid is evident from the mass spectrometer signal at the mass-to-charge ratio, m/z = 46 (HCOOH + ) as the ice sublimates. The detection of formic acid was confirmed using isotopically labeled water-d2 with carbon monoxide, leading to formic acid-d2 (DCOOD). The temporal fits of the reactants, reaction intermediates, and products elucidate two reaction pathways to formic acid in carbon monoxide-water ices. The reaction is induced by unimolecular decomposition of water forming atomic hydrogen (H) and the hydroxyl radical (OH). The dominating pathway to formic acid (HCOOH) was found to involve addition of suprathermal hydrogen atoms to carbon monoxide forming the formyl radical (HCO); the latter recombined with neighboring hydroxyl radicals to yield formic acid (HCOOH). To a lesser extent, hydroxyl radicals react with carbon monoxide to yield the hydroxyformyl radical (HOCO), which recombined with atomic hydrogen to produce formic acid. Similar processes are expected to produce formic acid within interstellar ices, cometary ices, and icy satellites, thus providing alternative processes for the generation of formic acid whose abundance in hot cores such as Sgr-B2 cannot be accounted for solely by gas-phase chemistry.

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“…In addition, we report new low wavenumber Raman data for β‐H 2 CO 3 . While this type of Raman spectra has been reported between 30 and 100 years ago for other carboxylic or dicarboxylic acids such as formic acid,77, 78, oxalic acid,76, 79–81 malonic acid57, 79, 82 or acetic acid,67 the smallest organic acid, containing only one C atom, has eluded attempts of Raman characterization until 2009 14. Because of the possible astrophysical relevance of carbonic acid2–15 and the possibility of exploring astrophysical objects such as Mars using Raman spectroscopy,83–88 the data are of importance in possibly identifying α‐H 2 CO 3 in outer space.…”

Section: Discussion/conclusionmentioning

confidence: 73%

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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The Raman and IR spectra of HCOOH and DCOOD crystals at low temperatures

Cited by 27 publications

References 13 publications

Potential energy curves in complementary base pairs and in model hydrogen bonded systems

Potential energy curves in complementary base pairs and in model hydrogen bonded systems

Laboratory Studies on the Formation of Formic Acid (Hcooh) in Interstellar and Cometary Ices

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

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