IR-induced conformer interconversion processes of glycolaldehyde in low-temperature matrices, and ab initio calculations on the energetics and vibrational frequencies of the conformers

Aspiala, Antero; Murto, Juhani; Stén, Pekka

doi:10.1016/0301-0104(86)87108-7

Cited by 35 publications

(50 citation statements)

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“…Although having similar chemical composition, glycolaldehyde and hydroxyacetone have rather different equipotential energy surface judging by the ones calculated by ab initio methods [14], [27] and [28]. We define as τ 1 the CH 2 O torsional angle around C 1 -C 2 bond, and as τ 2 the OH torsional angle around C 1 -O 3 bond.…”

Section: Resultsmentioning

confidence: 99%

“…We define as τ 1 the CH 2 O torsional angle around C 1 -C 2 bond, and as τ 2 the OH torsional angle around C 1 -O 3 bond. In the notation of reference [14] we denote cis conformation with respect to τ 1 with big letter C, and cis conformation with respect to τ 2 with small letter c. In the same manner trans conformers are denoted with T and t. For both molecules the most stable conformer is the one where hydroxyl and carbonyl group are in cis position (as shown in Fig. 4 and Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The greatest to 859 cm −1 infrared band [13], and in Ar matrix to 749 cm −1 band for Cc conformer [14]. The band at 535 cm Cc conformer [14].…”

Section: Glycoladehydementioning

confidence: 94%

“…At present there exist differences in the assignment of glycolaldehyde bands-Michelsen and Klaboe [13] based their tentative assignment on the infrared spectrum of vapor, while Aspiala et al [14] studied glycolaldehyde in Ar, Kr and Xe matrices by infrared spectroscopy. The greatest to 859 cm −1 infrared band [13], and in Ar matrix to 749 cm −1 band for Cc conformer [14].…”

Section: Glycoladehydementioning

confidence: 99%

“…The symmetry of these crystal phases as well as molecular conformation in each of them has not been determined yet by X ray crystallography, but the infrared and Raman study of Kobayashi et al [12] suggests the trans axial position of two OH groups in the phase α, and their equatorial position in the phase β. Previous research on glycolaldehyde that employed vibrational sectroscopy includes the work of Michelsen and Klaboe [13], infrared matrix isolation study of Aspiala et al [14], and, more recently, Yaylayan et al studied transformation of glycolaldehyde with temperature and in different solvents [15]. Quite a few NMR studies were done on glycolaldehyde [9], [10], [11], [16], [17], [18] and [19] and one on hydroxyacetone in aqueous solutions [20].…”

Section: Introductionmentioning

confidence: 99%

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Vibrational analysis of hydroxyacetone

Mohaček-Grošev

2005

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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In order to be able to fully understand the vibrational dynamics of monosaccharide sugars, we started with hydroxyacetone CH 2 OHCOCH 3, and glycolaldehyde CH 2 OHCOH, which are among the smallest molecules that contain hydroxyl and carbonyl group on neighboring carbon atoms. This sterical configuration is characteristic for saccharides and determines their biochemical activity. In this work vibrational analysis of hydroxyacetone was undertaken by performing the normal coordinate analysis for glycolaldehyde first, and transferring these force constants to hydroxyacetone. The observed Raman and infrared bands for 90 wt.% solution of hydroxyacetone in water (acetol) were used as a first approximation for the bands of free hydroxyacetone. The number of observed Raman and infrared bands for acetol exceeds the number of calculated values for the most stable hydroxyacetone conformer with C s symmetry, which suggests more than one conformer of hydroxyacetone in water solution. In particular, there are two bands both in infrared (1083 and 1057 cm −1 ) and in Raman spectrum (1086.5 and 1053 cm −1 ) that are assigned to the CO stretching mode and this is one of the indicators of several hydroxyacetone conformers in the solution. Additional information was obtained from low temperature Raman spectra: at 240 K a broad assymmetric band centered around 280 cm −1 appears, suggesting a disorder in the orientation of hydroxyl groups. Glassy state forms at ∼150 K. The broad band at 80 cm −1 is assigned to frozen torsions of hydroxymethyl groups.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…The greatest to 859 cm −1 infrared band [13], and in Ar matrix to 749 cm −1 band for Cc conformer [14]. The band at 535 cm Cc conformer [14].…”

Section: Glycoladehydementioning

confidence: 94%

Section: Glycoladehydementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Vibrational analysis of hydroxyacetone

Mohaček-Grošev

2005

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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Molecular Recognition in Glycolaldehyde, the Simplest Sugar: Two Isolated Hydrogen Bonds Win Over One Cooperative Pair

et al. 2012

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Carbohydrates are used in nature as molecular recognition tools. Understanding their conformational behavior upon aggregation helps in rationalizing the way in which cells and bacteria use sugars to communicate. Here, the simplest α-hydroxy carbonyl compound, glycolaldehyde, was used as a model system. It was shown to form compact polar C2-symmetric dimers with intermolecular O–H⋅⋅⋅O=C bonds, while sacrificing the corresponding intramolecular hydrogen bonds. Supersonic jet infrared (IR) and Raman spectra combined with high-level quantum chemical calculations provide a consistent picture for the preference over more typical hydrogen bond insertion and addition patterns. Experimental evidence for at least one metastable dimer is presented. A rotational spectroscopy investigation of these dimers is encouraged, also in view of astrophysical searches. The binding motif competition of aldehydic sugars might play a role in chirality recognition phenomena of more complex derivatives in the gas phase.

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Computational thermochemistry of glycolaldehyde

Bleda

Yavuz

Altun

et al. 2012

Int J of Quantum Chemistry

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We use a variant of the focal point analysis to refine estimates of the relative energies of the four low‐energy torsional conformers of glycolaldehyde. The most stable form is the cis‐cis structure which enjoys a degree of H‐bonding from hydroxyl H to carbonyl O; here dihedral angles τ1 (OCCO) and τ2 (CCOH) both are zero. We optimized structures in both CCSD(T)/aug‐cc‐pVDZ and aug‐cc‐pVTZ; the structures agree within 0.01 Å for bond lengths and 1.0 degrees for valence angles, but the larger basis brings the rotational constants closer to experimental values. According to our extrapolation of CCSD(T) energies evaluated in basis sets ranging to aug‐cc‐pVQZ the trans‐trans form (180°, 180°) has a relative energy of 12.6 kJ/mol. The trans‐gauche conformer (160°, ±75°) is situated at 13.9 kJ/mol and the cis‐trans form (0°, 180°) at 18.9 kJ/mol. Values are corrected for zero point vibrational energy by MP2/aug‐cc‐pVTZ frequencies. Modeling the vibrational spectra is best accomplished by MP2/aug‐cc‐pVTZ with anharmonic corrections. We compute the Watsonian parameters that define the theoretical vibrational‐rotational spectra for the four stable conformers, to assist the search for these species in the interstellar medium. Six transition states are located by G4 and CBS‐QB3 methods as well as extrapolation using energies for structures optimized in CCSD(T)/aug‐cc‐pVDZ structures. We use two isodesmic reactions with two well‐established thermochemical computational schemes G4 and CBS‐QB3 to estimate energy enthalpy and Gibbs energy of formation as well as the entropy of the gas phase system. Our extrapolated electronic energies of species appearing in the isodesmic reactions produce independent values of thermodynamic quantities consistent with G4 and CBS‐QB3. © 2013 Wiley Periodicals, Inc.

show abstract

IR-induced conformer interconversion processes of glycolaldehyde in low-temperature matrices, and ab initio calculations on the energetics and vibrational frequencies of the conformers

Cited by 35 publications

References 37 publications

Vibrational analysis of hydroxyacetone

Vibrational analysis of hydroxyacetone

Molecular Recognition in Glycolaldehyde, the Simplest Sugar: Two Isolated Hydrogen Bonds Win Over One Cooperative Pair

Computational thermochemistry of glycolaldehyde

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