The rich and complex potential energy surface of the ethanol dimer

Vargas-Caamal, Alba; Ortíz‐Chi, Filiberto; Moreno, Diego A.; Restrepo, Albeiro; Merino, Gabriel; Cabellos, José Luis

doi:10.1007/s00214-015-1615-9

Cited by 29 publications

(28 citation statements)

References 27 publications

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“…There have been several theoretical and experimental investigations of ethanol dimer [5][6][7][8][9][10][11][12][13][14][15][16] . Initial vibrational studies using molecular beam depletion 5 , FTIR 6 and cavity ring-down spectroscopy 7 provided evidence for up to four conformations, although it was not possible to assign spectral features to individual conformers.…”

Section: Introductionmentioning

confidence: 99%

“…Conformational identification was achieved by Hearn et al 8 , who observed three conformers of ethanol dimer and assigned them as the g+g+, g+t, and g−t (following the nomenclature above) using high resolution Fourier transform microwave spectroscopy. In addition, various theoretical calculations 7,8,9,10,11,12 have shown the complexity of the potential energy between the many lower-energy conformations and makes it difficult to predict molecular properties accurately. One of the persistent questions in the study of ethanol dimer was the identity of the lowest energy form.…”

Section: Introductionmentioning

confidence: 99%

“…One of the persistent questions in the study of ethanol dimer was the identity of the lowest energy form. Theoretical calculations originally predicted it to correspond to the tt species 9 , but later calculations agreed on the homochiral g+g+ configuration as the global minimum 10,11,12 . This makes ethanol dimer an interesting example of chirality synchronization 13 , where two transiently chiral ethanol molecules adjust to each other's handedness.…”

Section: Introductionmentioning

confidence: 99%

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Ethanol dimer: Observation of three new conformers by broadband rotational spectroscopy

Loru

Peña

Sanz

2017

Journal of Molecular Spectroscopy

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ethanol dimer: Observation of three new conformers by broadband rotational spectroscopy

Loru

Peña

Sanz

2017

Journal of Molecular Spectroscopy

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“…[2][3][4] Most of the investigations performed on ethanol clusters are limited to the ethanol dimer due to difficulties arising from the exploration of the potential energy surfaces (PESs) of the ethanol clusters. [2,3,[5][6][7][8][9][10][11] Reliable investigations performed on the ethanol dimer,…”

mentioning

confidence: 99%

“…Consequently, 153 local minima have been located by Vargas-Caamal and coworkers [10] on the PES of the ethanol dimer within 6.5 kcal/mol. This huge number of local minima on the PES of the ethanol dimer highlights the complexity of the exploration of ethanol clusters larger than the dimer.…”

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confidence: 99%

Theoretical infrared spectrum of the ethanol hexamer

Malloum

Fifen

Conradie

2020

Int J of Quantum Chemistry

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The hydrogen bond network of ethanol clusters is among the most complex hydrogen bond networks of molecular clusters. One of the reasons of its complexity arises from the number of possible ethanol monomers (there are three isoenergetic isomers of the ethanol monomer). This leads to difficulties in the exploration of potential energy surfaces (PESs) of ethanol clusters. In this work, we have explored the PES of the ethanol hexamer at the MP2/aug-cc-pVDZ level of theory. We have provided structures and their relative stability at 0 K and for temperatures ranging from 20 to 400 K in the gas phase. These structures are used to compute the theoretical infrared (IR) spectrum of the ethanol hexamer at the MP2/aug-cc-pVDZ level of theory. As a result, 98 different structures have been investigated, and six isomers are reported to be the most isoenergetically stable structures of the ethanol hexamer. These isomers are folded cyclic structures in which the stability is enhanced by the implication of CHÁ Á ÁO interactions. Our investigations show that the PES of the ethanol hexamer is very flat, yielding several isoenergetic structures. Furthermore, we have noted that several isomers contribute to the population of the ethanol hexamer at high temperatures. As far as the IR spectroscopic study is concerned, we have found that the IR spectra of the most stable structures are in good agreement with the experiment.Considering this agreement, these structures are used to assign the experimental peaks in the CH-stretching region. We concluded that the stability of the structures of the ethanol hexamer is related both to OHÁ Á ÁO hydrogen bonds and CHÁ Á ÁO interactions. Overall, we have found that the IR spectrum of the ethanol hexamer, calculated from the contribution of all the possible stable structures weighted by their probability, excellently reproduce the experimental spectrum of the ethanol hexamer. K E Y W O R D S ethanol clusters, ethanol hexamer, infrared spectrum, relative population, Voigt profile 1 | INTRODUCTIONLiquid ethanol has important applications in industries, and it is widely used as a solvent in chemical processes. Besides, ethanol has many applications in medicine and pharmacology. [1] Understanding of some properties of liquid ethanol is related to the hydrogen bond networks of ethanol clusters (EtOH) n . The hydrogen bond networks of the ethanol clusters are among the most complex hydrogen bond networks in molecular clusters. One of the reasons of this complexity is the high number of possible stable structures of the ethanol monomer (there are three isoenergetic isomers of the ethanol monomer: gauche−, trans, and gauche+ related to the value of the CCOH dihedral angles −60 , 180 , and +60 , respectively). [2][3][4] Most of the investigations performed on ethanol clusters are limited to the ethanol dimer due to difficulties arising from the exploration of the potential energy surfaces (PESs) of the ethanol clusters. [2,3,[5][6][7][8][9][10][11] Reliable investigations performed on the ethanol dimer,

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Acid Dissociation in (HX)_n(H₂O)_nClusters (X=F, Cl, Br, I;n=2, 3)**

et al. 2022

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In this work, we analyze the interactions between two or three hydrogen halide molecules and the same number of water moieties through a systematic exploration of their potential energy surfaces. Our results indicate that the most stable HF and HCl aggregates do not experience dissociation of any of the acid fragments, even with three water molecules. In contrast, in the HBr and HI clusters, one of the acid fragments does dissociate. While the global minimum of (HBr) 3 (H 2 O) 3 is a hydrogen-bridged bihalide anion (BrHBr À ), which is persistent at temperatures up to 203 K, the lowest energy structure of (HI) 3 (H 2 O) 3 has a separated ion pair, but the motif with a bihalide anion (IHI À ) is only 0.2 kcal mol À 1 above the global minimum. Among the more stable structures is a broad spectrum of contacts, including water⋯water, HX⋯water, and HX⋯HX hydrogen bonds, halogen bonds, ionic and long-range X⋯H contacts.

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The rich and complex potential energy surface of the ethanol dimer

Cited by 29 publications

References 27 publications

Ethanol dimer: Observation of three new conformers by broadband rotational spectroscopy

Ethanol dimer: Observation of three new conformers by broadband rotational spectroscopy

Theoretical infrared spectrum of the ethanol hexamer

Acid Dissociation in (HX)_n(H₂O)_nClusters (X=F, Cl, Br, I;n=2, 3)**

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The rich and complex potential energy surface of the ethanol dimer

Cited by 29 publications

References 27 publications

Ethanol dimer: Observation of three new conformers by broadband rotational spectroscopy

Ethanol dimer: Observation of three new conformers by broadband rotational spectroscopy

Theoretical infrared spectrum of the ethanol hexamer

Acid Dissociation in (HX)n(H2O)nClusters (X=F, Cl, Br, I;n=2, 3)**

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Product

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Acid Dissociation in (HX)_n(H₂O)_nClusters (X=F, Cl, Br, I;n=2, 3)**