Self-organization of 1-methylnaphthalene on the surface of artificial snow grains: A combined experimental-computational approach

Dominik Heger, Dana Nachtigallová, František Surman, Ján Krausko, Beata Magyarová, Miroslav Brumovský, Miroslav Rubeš, Ivan Gladich, Petr Klán

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

A combined experimental-computational approach was used to study the self-organization and microenvironment of 1-methylnaphthalene (1MN) deposited on the surface of artificial snow grains from vapors at 238 K. The specific surface area of this snow (1.1 × 10 4 cm 2 g -1), produced by spraying very fine droplets of pure water from a nebulizer into liquid nitrogen, was determined using valerophenone photochemistry to estimate the surface coverage by 1MN. Fluorescence spectroscopy at 77 K, in combination with molecular dynamics simulations, and density functional theory (DFT) and second-order coupled cluster (CC2) calculations, provided evidence for the occurrence of ground- and excited-state complexes (excimers) and other associates of 1MN on the snow grains' surface. Only weak excimer fluorescence was observed for a loading of 5 × 10 -6 mol kg -1, which is ∼2-3 orders of magnitude below monolayer coverage. However, the results indicate that the formation of excimers is favored at higher surface loadings (>5 × 10 -5 mol kg -1), albeit still being below monolayer coverage. The calculations of excited states of monomer and associated moieties suggested that a parallel-displaced arrangement is responsible for the excimer emission observed experimentally, although some other associations, such as T-shape dimer structures, which do not provide excimer emission, can still be relatively abundant at this surface concentration. The hydrophobic 1MN molecules, deposited on the ice surface, which is covered by a relatively flexible quasi-liquid layer at 238 K, are then assumed to be capable of dynamic motion resulting in the formation of energetically preferred associations to some extent. The environmental implications of organic compounds' deposition on snow grains and ice are discussed.

Original languageEnglish
Pages (from-to)11412-11422
Number of pages11
JournalJournal of Physical Chemistry A
Volume115
Issue number41
DOIs
Publication statusPublished - 20 Oct 2011
Externally publishedYes

Fingerprint

Snow
snow
excimers
Ice
Photochemistry
Excited states
Nebulizers and Vaporizers
Monolayers
Fluorescence Spectrometry
Molecular Dynamics Simulation
ice
Nitrogen
T shape
Fluorescence
Photochemical reactions
Fluorescence spectroscopy
fluorescence
Liquid nitrogen
Spraying
Organic compounds

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Heger, D., Nachtigallová, D., Surman, F., Krausko, J., Magyarová, B., Brumovský, M., ... Klán, P. (2011). Self-organization of 1-methylnaphthalene on the surface of artificial snow grains: A combined experimental-computational approach. Journal of Physical Chemistry A, 115(41), 11412-11422. https://doi.org/10.1021/jp205627a

Self-organization of 1-methylnaphthalene on the surface of artificial snow grains : A combined experimental-computational approach. / Heger, Dominik; Nachtigallová, Dana; Surman, František; Krausko, Ján; Magyarová, Beata; Brumovský, Miroslav; Rubeš, Miroslav; Gladich, Ivan; Klán, Petr.

In: Journal of Physical Chemistry A, Vol. 115, No. 41, 20.10.2011, p. 11412-11422.

Research output: Contribution to journalArticle

Heger, D, Nachtigallová, D, Surman, F, Krausko, J, Magyarová, B, Brumovský, M, Rubeš, M, Gladich, I & Klán, P 2011, 'Self-organization of 1-methylnaphthalene on the surface of artificial snow grains: A combined experimental-computational approach', Journal of Physical Chemistry A, vol. 115, no. 41, pp. 11412-11422. https://doi.org/10.1021/jp205627a
Heger, Dominik ; Nachtigallová, Dana ; Surman, František ; Krausko, Ján ; Magyarová, Beata ; Brumovský, Miroslav ; Rubeš, Miroslav ; Gladich, Ivan ; Klán, Petr. / Self-organization of 1-methylnaphthalene on the surface of artificial snow grains : A combined experimental-computational approach. In: Journal of Physical Chemistry A. 2011 ; Vol. 115, No. 41. pp. 11412-11422.
@article{5b8367b0c7f147339c53ecaf50db31b3,
title = "Self-organization of 1-methylnaphthalene on the surface of artificial snow grains: A combined experimental-computational approach",
abstract = "A combined experimental-computational approach was used to study the self-organization and microenvironment of 1-methylnaphthalene (1MN) deposited on the surface of artificial snow grains from vapors at 238 K. The specific surface area of this snow (1.1 × 10 4 cm 2 g -1), produced by spraying very fine droplets of pure water from a nebulizer into liquid nitrogen, was determined using valerophenone photochemistry to estimate the surface coverage by 1MN. Fluorescence spectroscopy at 77 K, in combination with molecular dynamics simulations, and density functional theory (DFT) and second-order coupled cluster (CC2) calculations, provided evidence for the occurrence of ground- and excited-state complexes (excimers) and other associates of 1MN on the snow grains' surface. Only weak excimer fluorescence was observed for a loading of 5 × 10 -6 mol kg -1, which is ∼2-3 orders of magnitude below monolayer coverage. However, the results indicate that the formation of excimers is favored at higher surface loadings (>5 × 10 -5 mol kg -1), albeit still being below monolayer coverage. The calculations of excited states of monomer and associated moieties suggested that a parallel-displaced arrangement is responsible for the excimer emission observed experimentally, although some other associations, such as T-shape dimer structures, which do not provide excimer emission, can still be relatively abundant at this surface concentration. The hydrophobic 1MN molecules, deposited on the ice surface, which is covered by a relatively flexible quasi-liquid layer at 238 K, are then assumed to be capable of dynamic motion resulting in the formation of energetically preferred associations to some extent. The environmental implications of organic compounds' deposition on snow grains and ice are discussed.",
author = "Dominik Heger and Dana Nachtigallov{\'a} and František Surman and J{\'a}n Krausko and Beata Magyarov{\'a} and Miroslav Brumovsk{\'y} and Miroslav Rubeš and Ivan Gladich and Petr Kl{\'a}n",
year = "2011",
month = "10",
day = "20",
doi = "10.1021/jp205627a",
language = "English",
volume = "115",
pages = "11412--11422",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "41",

}

TY - JOUR

T1 - Self-organization of 1-methylnaphthalene on the surface of artificial snow grains

T2 - A combined experimental-computational approach

AU - Heger, Dominik

AU - Nachtigallová, Dana

AU - Surman, František

AU - Krausko, Ján

AU - Magyarová, Beata

AU - Brumovský, Miroslav

AU - Rubeš, Miroslav

AU - Gladich, Ivan

AU - Klán, Petr

PY - 2011/10/20

Y1 - 2011/10/20

N2 - A combined experimental-computational approach was used to study the self-organization and microenvironment of 1-methylnaphthalene (1MN) deposited on the surface of artificial snow grains from vapors at 238 K. The specific surface area of this snow (1.1 × 10 4 cm 2 g -1), produced by spraying very fine droplets of pure water from a nebulizer into liquid nitrogen, was determined using valerophenone photochemistry to estimate the surface coverage by 1MN. Fluorescence spectroscopy at 77 K, in combination with molecular dynamics simulations, and density functional theory (DFT) and second-order coupled cluster (CC2) calculations, provided evidence for the occurrence of ground- and excited-state complexes (excimers) and other associates of 1MN on the snow grains' surface. Only weak excimer fluorescence was observed for a loading of 5 × 10 -6 mol kg -1, which is ∼2-3 orders of magnitude below monolayer coverage. However, the results indicate that the formation of excimers is favored at higher surface loadings (>5 × 10 -5 mol kg -1), albeit still being below monolayer coverage. The calculations of excited states of monomer and associated moieties suggested that a parallel-displaced arrangement is responsible for the excimer emission observed experimentally, although some other associations, such as T-shape dimer structures, which do not provide excimer emission, can still be relatively abundant at this surface concentration. The hydrophobic 1MN molecules, deposited on the ice surface, which is covered by a relatively flexible quasi-liquid layer at 238 K, are then assumed to be capable of dynamic motion resulting in the formation of energetically preferred associations to some extent. The environmental implications of organic compounds' deposition on snow grains and ice are discussed.

AB - A combined experimental-computational approach was used to study the self-organization and microenvironment of 1-methylnaphthalene (1MN) deposited on the surface of artificial snow grains from vapors at 238 K. The specific surface area of this snow (1.1 × 10 4 cm 2 g -1), produced by spraying very fine droplets of pure water from a nebulizer into liquid nitrogen, was determined using valerophenone photochemistry to estimate the surface coverage by 1MN. Fluorescence spectroscopy at 77 K, in combination with molecular dynamics simulations, and density functional theory (DFT) and second-order coupled cluster (CC2) calculations, provided evidence for the occurrence of ground- and excited-state complexes (excimers) and other associates of 1MN on the snow grains' surface. Only weak excimer fluorescence was observed for a loading of 5 × 10 -6 mol kg -1, which is ∼2-3 orders of magnitude below monolayer coverage. However, the results indicate that the formation of excimers is favored at higher surface loadings (>5 × 10 -5 mol kg -1), albeit still being below monolayer coverage. The calculations of excited states of monomer and associated moieties suggested that a parallel-displaced arrangement is responsible for the excimer emission observed experimentally, although some other associations, such as T-shape dimer structures, which do not provide excimer emission, can still be relatively abundant at this surface concentration. The hydrophobic 1MN molecules, deposited on the ice surface, which is covered by a relatively flexible quasi-liquid layer at 238 K, are then assumed to be capable of dynamic motion resulting in the formation of energetically preferred associations to some extent. The environmental implications of organic compounds' deposition on snow grains and ice are discussed.

UR - http://www.scopus.com/inward/record.url?scp=80054688829&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80054688829&partnerID=8YFLogxK

U2 - 10.1021/jp205627a

DO - 10.1021/jp205627a

M3 - Article

C2 - 21882845

AN - SCOPUS:80054688829

VL - 115

SP - 11412

EP - 11422

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 41

ER -