FTIR spectra and conformational structure of deutero-β-alanine isolated in argon matrices

Stepanian, S. G.; Ivanov, А. Yu.; Adamowicz, Ludwik

doi:10.1016/j.jms.2015.12.010

Cited by 9 publications

(8 citation statements)

References 67 publications

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“…The correct description of the relative energetics is challenging for semilocal as well as hybrid functionals, as is seen by the different energetic ordering between PBE and B3LYP. Many theoretical studies report conformer V to be the second most stable conformer after conformer I. − ,, Higher-order chemical theory like Møller–Plesset (MP2) finds conformer V to be most stable , but the second most stable if ZPE is taken into account. , Inclusion of ZPE is in favor of conformer I also in PBE and TS09 but does not change their energetic ordering. Analysis of the experimental IR spectrum reveals that the population of conformer V is low. , Due to this preference of conformer V in PBE and its structural tendency to facilitate proton transfer from the carboxyl to the amide group to form Z , we will still consider the presence of conformer V in the following.…”

Section: Resultsmentioning

confidence: 99%

“…[26][27][28]30,45 Higher-order chemical theory like Møller−Plesset (MP2) finds conformer V to be most stable 28,46 but the second most stable if ZPE is taken into account. 28,29 Inclusion of ZPE is in favor of conformer I also in PBE and TS09 but does not change their energetic ordering. Analysis of the experimental IR spectrum reveals that the population of conformer V is low.…”

Section: Resultsmentioning

confidence: 99%

“…The conformer’s lifetime is dependent on extraterrestrial environments, specifically the photostability against UV radiation . There are many computational studies on the most stable conformers of BA both at zero Kelvin and room temperature, where various energetically similar conformers have been found. − The presence of different conformers was experimentally confirmed by rotational and IR spectra. − …”

Section: Introductionmentioning

confidence: 95%

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Stability and IR Spectroscopy of Zwitterionic Form of β-Alanine in Water Clusters

et al. 2019

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Amino acids are the building blocks of proteins, and their detection in outer space thus has implications on the origin of life. They form a zwitterionic structure in aqueous environments while adopting a neutral configuration in the gas phase. We perform an experimental and computational study on the number of water molecules needed for zwitterion formation of β-alanine. Our density functional theory investigation reveals that a minimum of five water molecules are required to form and stabilize the zwitterion. A characteristic connecting water molecule located between the COO– and NH3 + groups is found to enhance the stability. This water molecule is also involved in a characteristic infrared active vibration at ≈1560 cm–1, which is slightly shifted with the number of surrounding water molecules and is located in a spectral region outside of water vibrations. A corresponding infrared signal is found in high-resolution experimental spectra of β-alanine and water in a solid para-hydrogen matrix.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

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Stability and IR Spectroscopy of Zwitterionic Form of β-Alanine in Water Clusters

et al. 2019

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“…3 However, the average difference between the experimental and theoretical conformer frequencies of flexible molecules is about 10 cm À1 . 4,29,30 At the same time, for many types of vibrations the differences between the frequencies of several conformers do not exceed 5 cm À1 , which makes it difficult to form a reliable interpretation of the experimental spectra. In the case of using the method of isolating the molecules in inert gas matrices, the reason behind the divergence of the experimental and theoretical vibration frequencies is the influence the matrix environment has on the structure and spectra of the isolated molecules.…”

Section: Conformer Population In Ftir Spectra Of N-acetylglycine In Amentioning

confidence: 99%

“…This difference cannot be reduced to less than 5-10 cm À1 even when using the most accurate calculation methods, including those that account for the anharmonicity of the vibrations and the polynomial scaling of the calculated frequencies. [4][5][6] In order to solve this problem, it is necessary to use the results from calculations obtained for a model system that includes both the test molecule and the inert gas atoms, when analyzing the experimental IR spectra. First, the calculations were conducted for the simplest model systems that included only one inert gas atom.…”

Section: Introductionmentioning

confidence: 99%

Effect of low-temperature argon matrices on the IR spectra and structure of flexible N-acetylglycine molecules

Stepanian

Ivanov

Adamowicz³

2016

Low Temperature Physics

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A study of how the matrix environment impacts the structure and IR spectra of N-acetylglycine conformers. The conformational composition of this compound is determined according to an analysis of the FTIR spectra of N-acetylglycine isolated in low temperature argon matrices. Bands of three N-acetylglycine conformers are identified based on the spectra: one major and two minor. The structure of all observed conformers is stabilized by different intramolecular hydrogen bonds. The Gibbs free energies of the conformers were calculated (CCSD(T)/CBS method), and these energy values were used to calculate conformer population at a temperature of 360 K, of which 85.3% belonged to the main conformer, and 9.6% and 5.1% to the minor conformers. We also determined the size and shape of the cavities that form when the N-acetylglycine conformers are embedded in the argon crystal during matrix deposition. It is established that the most energetically favorable cavity for the planar main conformer is the cavity that forms when 7 argon atoms are replaced. At the same time, bulky minor conformers were embedded into cavities that correspond to 8 removed argon atoms. We calculated the complexation energy between argon clusters and conformers, and the deformation energy of the argon crystal and the N-acetylglycine conformers. The matrix-induced shifts to the conformer oscillation frequency are calculated.

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A DFT Study on the Tautomerization of β‐Alanine

Yamabe,

Tsuchida,

Yamazaki

2024

ChemistrySelect

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Tautomerization paths of β‐alanine with explicit inclusion of water molecules, (H2O)n, were investigated by DFT calculations, wB97X‐D/6‐311+G(d,p) SCRF=PCM. Structures of zwitterions of the alanine of trans (t−) and gauche (g−) conformations with seven water molecules (n=7) were examined. On the basis of those geometries, elementary processes of the tautomerization were investigated. For the t‐conformer of β‐alanine, reaction models of n=8, 10, 14, 18 and 24 were scrutinized. While reaction processes are slightly modified with different number of water molecules, n=18 and 24 models afforded three elementary reactions, t‐alanine with cis‐COOH→t‐ion pair→t‐alanine with trans‐COOH→t‐zwitterion. The (H2O)4 hydrogen‐bonded chain participates in the reactions. For the g‐conformer, models of n=7, 10, 14 and 18 were investigated, and the tautomerization was found to take place concertedly via (H2O)2.

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FTIR spectra and conformational structure of deutero-β-alanine isolated in argon matrices

Cited by 9 publications

References 67 publications

Stability and IR Spectroscopy of Zwitterionic Form of β-Alanine in Water Clusters

Stability and IR Spectroscopy of Zwitterionic Form of β-Alanine in Water Clusters

Effect of low-temperature argon matrices on the IR spectra and structure of flexible N-acetylglycine molecules

A DFT Study on the Tautomerization of β‐Alanine

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