Spectroscopic Properties of Benzene at the Air–Ice Interface: A
Combined Experimental–Computational Approach

J 2014

Spectroscopic Properties of Benzene at the Air–Ice Interface: A Combined Experimental–Computational Approach

KANIA, Rafal Józef, Joseph K'ekuboni MALONGWE, Dana NACHTIGALLOVÁ, Ján KRAUSKO, Ivan GLADICH et. al.

Základní údaje

Originální název

Spectroscopic Properties of Benzene at the Air–Ice Interface: A Combined Experimental–Computational Approach

Autoři

KANIA, Rafal Józef (616 Polsko, domácí), Joseph K'ekuboni MALONGWE (180 Konžská demokratická republika, domácí), Dana NACHTIGALLOVÁ (203 Česká republika), Ján KRAUSKO (703 Slovensko, domácí), Ivan GLADICH (203 Česká republika), Martina ROESELOVÁ (203 Česká republika), Dominik HEGER (203 Česká republika, domácí) a Petr KLÁN (203 Česká republika, garant, domácí)

Vydání

Journal of Physical Chemistry A, 2014, 1089-5639

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10401 Organic chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 2.693

Kód RIV

RIV/00216224:14310/14:00074347

Organizační jednotka

Přírodovědecká fakulta

DOI

http://dx.doi.org/10.1021/jp501094n

UT WoS

000341337800041

Klíčová slova anglicky

Ice; snow; benzene; spectroscopy; calculations

Štítky

AKR, rivok

Změněno: 19. 2. 2015 13:30, prof. RNDr. Petr Klán, Ph.D.

Anotace

V originále

A combined experimental and computational approach was used to study the spectroscopic properties of benzene at the ice–air interface at 253 and 77 K in comparison with its spectroscopic behavior in aqueous solutions. Benzene-contaminated ice samples were prepared either by shock-freezing of benzene aqueous solutions or by benzene vapor-deposition on pure ice grains and examined using UV diffuse reflectance and emission spectroscopies. Neither the absorption nor excitation nor emission spectra provided unambiguous evidence of benzene associates on the ice surface even at a higher surface coverage. Only a small increase in the fluorescence intensity in the region above 290 nm found experimentally might be associated with formation of benzene excimers perturbed by the interaction with the ice surface as shown by ADC(2) excited-state calculations. The benzene associates were found by MD simulations and ground-state DFT calculations, although not in the arrangement that corresponds to the excimer structures. Our experimental results clearly demonstrated that the energy of the S0-S1 electronic transition of benzene is not markedly affected by the phase change or the microenvironment at the ice–air interface and its absorption is limited to the wavelengths below 268 nm. Neither benzene interactions with the water molecules of ice nor the formation of dimers and microcrystals at the air–ice interface thus causes any substantial bathochromic shift in its absorption spectrum. Such a critical evaluation of the photophysical properties of organic contaminants of snow and ice is essential for predictions and modeling of chemical processes occurring in polar regions.

Návaznosti

EE2.3.30.0037, projekt VaV

Název: Zaměstnáním nejlepších mladých vědců k rozvoji mezinárodní spolupráce

GAP503/10/0947, projekt VaV

Název: Důsledky fotochemické aktivity organických polutantů v polárních oblastech

Investor: Grantová agentura ČR, Důsledky fotochemické aktivity organických polutantů v polárních oblastech

LO1214, projekt VaV

Název: Centrum pro výzkum toxických látek v prostředí (Akronym: RECETOX)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Centrum pro výzkum toxických látek v prostředí

Citovat

KANIA, Rafal Józef, Joseph K'ekuboni MALONGWE, Dana NACHTIGALLOVÁ, Ján KRAUSKO, Ivan GLADICH, Martina ROESELOVÁ, Dominik HEGER a Petr KLÁN. Spectroscopic Properties of Benzene at the Air–Ice Interface: A Combined Experimental–Computational Approach. Journal of Physical Chemistry A. 2014, roč. 118, č. 35, s. 7535-7547. ISSN 1089-5639. Dostupné z: https://dx.doi.org/10.1021/jp501094n.

@article{1217789,
   author = {Kania, Rafal Józef and Malongwe, Joseph K'ekuboni and Nachtigallová, Dana and Krausko, Ján and Gladich, Ivan and Roeselová, Martina and Heger, Dominik and Klán, Petr},
   article_number = {35},
   doi = {http://dx.doi.org/10.1021/jp501094n},
   keywords = {Ice; snow; benzene; spectroscopy; calculations},
   language = {eng},
   issn = {1089-5639},
   journal = {Journal of Physical Chemistry A},
   title = {Spectroscopic Properties of Benzene at the Air–Ice Interface: A Combined Experimental–Computational Approach},
   url = {http://pubs.acs.org/doi/abs/10.1021/jp501094n},
   volume = {118},
   year = {2014}
}

TY  - JOUR
ID  - 1217789
AU  - Kania, Rafal Józef - Malongwe, Joseph K'ekuboni - Nachtigallová, Dana - Krausko, Ján - Gladich, Ivan - Roeselová, Martina - Heger, Dominik - Klán, Petr
PY  - 2014
TI  - Spectroscopic Properties of Benzene at the Air–Ice Interface: A Combined Experimental–Computational Approach
JF  - Journal of Physical Chemistry A
VL  - 118
IS  - 35
SP  - 7535-7547
EP  - 7535-7547
SN  - 10895639
KW  - Ice
KW  - snow
KW  - benzene
KW  - spectroscopy
KW  - calculations
UR  - http://pubs.acs.org/doi/abs/10.1021/jp501094n
N2  - A combined experimental and computational approach was used to study the spectroscopic properties of benzene at the ice–air interface at 253 and 77 K in comparison with its spectroscopic behavior in aqueous solutions. Benzene-contaminated ice samples were prepared either by shock-freezing of benzene aqueous solutions or by benzene vapor-deposition on pure ice grains and examined using UV diffuse reflectance and emission spectroscopies. Neither the absorption nor excitation nor emission spectra provided unambiguous evidence of benzene associates on the ice surface even at a higher surface coverage. Only a small increase in the fluorescence intensity in the region above 290 nm found experimentally might be associated with formation of benzene excimers perturbed by the interaction with the ice surface as shown by ADC(2) excited-state calculations. The benzene associates were found by MD simulations and ground-state DFT calculations, although not in the arrangement that corresponds to the excimer structures. Our experimental results clearly demonstrated that the energy of the S0-S1 electronic transition of benzene is not markedly affected by the phase change or the microenvironment at the ice–air interface and its absorption is limited to the wavelengths below 268 nm. Neither benzene interactions with the water molecules of ice nor the formation of dimers and microcrystals at the air–ice interface thus causes any substantial bathochromic shift in its absorption spectrum. Such a critical evaluation of the photophysical properties of organic contaminants of snow and ice is essential for predictions and modeling of chemical processes occurring in polar regions.
ER  -

KANIA, Rafal Józef, Joseph K'ekuboni MALONGWE, Dana NACHTIGALLOVÁ, Ján KRAUSKO, Ivan GLADICH, Martina ROESELOVÁ, Dominik HEGER a Petr KLÁN. Spectroscopic Properties of Benzene at the Air–Ice Interface: A Combined Experimental–Computational Approach. \textit{Journal of Physical Chemistry A}. 2014, roč.~118, č.~35, s.~7535-7547. ISSN~1089-5639. Dostupné z: https://dx.doi.org/10.1021/jp501094n.

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