Closed-Shell Organic Compounds Might Form Dimers at the Surface of Molecular Clusters

Viivi Hirvonen, Nanna Myllys, Theo Kurtén, Jonas Elm

Tutkimustuotos: ArtikkelijulkaisuArtikkeliTieteellinenvertaisarvioitu

Kuvaus

The role of covalently bound dimer formation is studied using highlevel quantum chemical methods. Reaction free energy profiles for dimer formation between common oxygen-containing functional groups are calculated, and based on the Gibbs free energy differences between transition states and reactants, we show that none of the studied two-component gas-phase reactions are kinetically feasible at 298.15 K and 1 atm. Therefore, the catalyzing effect of water, base, or acid molecules is calculated, and sulfuric acid is identified to lower the activation free energies significantly. We find that the reactions yielding hemiacetal, peroxyhemiacetal, alpha-hydroxyester, and geminal diol products occur with activation free energies of less than 10 kcal/mol with sulfuric acid as a catalyst, indicating that these reactions could potentially take place on the surface of sulfuric acid clusters. Additionally, the formed dimer products bind stronger onto the pre-existing cluster than the corresponding reagent monomers do. This implies that covalent dimerization reactions stabilize the existing cluster thermodynamically and make it less likely to evaporate. However, the studied small organic compounds, which contain only one functional group, not able to form dimer are products that are stable against evaporation at atmospheric conditions. Calculations of dimer formation onto a cluster surface and the clustering ability of dimer products should be extended to large terpene oxidation products in order to estimate the real atmospheric significance.

Alkuperäiskielienglanti
LehtiJournal of Physical Chemistry A
Vuosikerta122
Numero6
Sivut1771-1780
Sivumäärä10
ISSN1089-5639
DOI - pysyväislinkit
TilaJulkaistu - 15 helmikuuta 2018
OKM-julkaisutyyppiA1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä, vertaisarvioitu

Tieteenalat

  • 114 Fysiikka
  • 116 Kemia

Lainaa tätä

Hirvonen, Viivi ; Myllys, Nanna ; Kurtén, Theo ; Elm, Jonas. / Closed-Shell Organic Compounds Might Form Dimers at the Surface of Molecular Clusters. Julkaisussa: Journal of Physical Chemistry A. 2018 ; Vuosikerta 122, Nro 6. Sivut 1771-1780.
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title = "Closed-Shell Organic Compounds Might Form Dimers at the Surface of Molecular Clusters",
abstract = "The role of covalently bound dimer formation is studied using highlevel quantum chemical methods. Reaction free energy profiles for dimer formation between common oxygen-containing functional groups are calculated, and based on the Gibbs free energy differences between transition states and reactants, we show that none of the studied two-component gas-phase reactions are kinetically feasible at 298.15 K and 1 atm. Therefore, the catalyzing effect of water, base, or acid molecules is calculated, and sulfuric acid is identified to lower the activation free energies significantly. We find that the reactions yielding hemiacetal, peroxyhemiacetal, alpha-hydroxyester, and geminal diol products occur with activation free energies of less than 10 kcal/mol with sulfuric acid as a catalyst, indicating that these reactions could potentially take place on the surface of sulfuric acid clusters. Additionally, the formed dimer products bind stronger onto the pre-existing cluster than the corresponding reagent monomers do. This implies that covalent dimerization reactions stabilize the existing cluster thermodynamically and make it less likely to evaporate. However, the studied small organic compounds, which contain only one functional group, not able to form dimer are products that are stable against evaporation at atmospheric conditions. Calculations of dimer formation onto a cluster surface and the clustering ability of dimer products should be extended to large terpene oxidation products in order to estimate the real atmospheric significance.",
keywords = "114 Physical sciences, AUTOXIDATION PRODUCT C6H8O7, DENSITY-FUNCTIONAL THEORY, SULFURIC-ACID, ATMOSPHERIC IMPLICATIONS, ALPHA-PINENE, ACCRETION REACTIONS, PARTICULATE MATTER, ORBITAL METHODS, OXALIC-ACID, BASIS-SETS, 116 Chemical sciences",
author = "Viivi Hirvonen and Nanna Myllys and Theo Kurt{\'e}n and Jonas Elm",
year = "2018",
month = "2",
day = "15",
doi = "10.1021/acs.jpca.7b11970",
language = "English",
volume = "122",
pages = "1771--1780",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
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Closed-Shell Organic Compounds Might Form Dimers at the Surface of Molecular Clusters. / Hirvonen, Viivi; Myllys, Nanna; Kurtén, Theo; Elm, Jonas.

julkaisussa: Journal of Physical Chemistry A, Vuosikerta 122, Nro 6, 15.02.2018, s. 1771-1780.

Tutkimustuotos: ArtikkelijulkaisuArtikkeliTieteellinenvertaisarvioitu

TY - JOUR

T1 - Closed-Shell Organic Compounds Might Form Dimers at the Surface of Molecular Clusters

AU - Hirvonen, Viivi

AU - Myllys, Nanna

AU - Kurtén, Theo

AU - Elm, Jonas

PY - 2018/2/15

Y1 - 2018/2/15

N2 - The role of covalently bound dimer formation is studied using highlevel quantum chemical methods. Reaction free energy profiles for dimer formation between common oxygen-containing functional groups are calculated, and based on the Gibbs free energy differences between transition states and reactants, we show that none of the studied two-component gas-phase reactions are kinetically feasible at 298.15 K and 1 atm. Therefore, the catalyzing effect of water, base, or acid molecules is calculated, and sulfuric acid is identified to lower the activation free energies significantly. We find that the reactions yielding hemiacetal, peroxyhemiacetal, alpha-hydroxyester, and geminal diol products occur with activation free energies of less than 10 kcal/mol with sulfuric acid as a catalyst, indicating that these reactions could potentially take place on the surface of sulfuric acid clusters. Additionally, the formed dimer products bind stronger onto the pre-existing cluster than the corresponding reagent monomers do. This implies that covalent dimerization reactions stabilize the existing cluster thermodynamically and make it less likely to evaporate. However, the studied small organic compounds, which contain only one functional group, not able to form dimer are products that are stable against evaporation at atmospheric conditions. Calculations of dimer formation onto a cluster surface and the clustering ability of dimer products should be extended to large terpene oxidation products in order to estimate the real atmospheric significance.

AB - The role of covalently bound dimer formation is studied using highlevel quantum chemical methods. Reaction free energy profiles for dimer formation between common oxygen-containing functional groups are calculated, and based on the Gibbs free energy differences between transition states and reactants, we show that none of the studied two-component gas-phase reactions are kinetically feasible at 298.15 K and 1 atm. Therefore, the catalyzing effect of water, base, or acid molecules is calculated, and sulfuric acid is identified to lower the activation free energies significantly. We find that the reactions yielding hemiacetal, peroxyhemiacetal, alpha-hydroxyester, and geminal diol products occur with activation free energies of less than 10 kcal/mol with sulfuric acid as a catalyst, indicating that these reactions could potentially take place on the surface of sulfuric acid clusters. Additionally, the formed dimer products bind stronger onto the pre-existing cluster than the corresponding reagent monomers do. This implies that covalent dimerization reactions stabilize the existing cluster thermodynamically and make it less likely to evaporate. However, the studied small organic compounds, which contain only one functional group, not able to form dimer are products that are stable against evaporation at atmospheric conditions. Calculations of dimer formation onto a cluster surface and the clustering ability of dimer products should be extended to large terpene oxidation products in order to estimate the real atmospheric significance.

KW - 114 Physical sciences

KW - AUTOXIDATION PRODUCT C6H8O7

KW - DENSITY-FUNCTIONAL THEORY

KW - SULFURIC-ACID

KW - ATMOSPHERIC IMPLICATIONS

KW - ALPHA-PINENE

KW - ACCRETION REACTIONS

KW - PARTICULATE MATTER

KW - ORBITAL METHODS

KW - OXALIC-ACID

KW - BASIS-SETS

KW - 116 Chemical sciences

U2 - 10.1021/acs.jpca.7b11970

DO - 10.1021/acs.jpca.7b11970

M3 - Article

VL - 122

SP - 1771

EP - 1780

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 6

ER -