Document Detail


Emergence of charge-transfer-to-solvent band in the absorption spectra of hydrogen halides on ice nanoparticles: spectroscopic evidence for acidic dissociation.
MedLine Citation:
PMID:  18507365     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Extensive ab initio calculations complemented by a photodissociation experiment at 193 nm elucidate the nature of hydrogen halide molecules bound on free ice nanoparticles. Electronic absorption spectra of small water clusters (up to 5 water molecules) and water clusters doped with hydrogen fluoride, hydrogen chloride and hydrogen bromide were calculated. The spectra were modeled at the time-dependent density functional (TDDFT) level of theory with the BHandHLYP functional using the reflection principle. We observe the emergence of a charge-transfer-to-solvent (CTTS) band in the absorption spectra upon the acidic dissociation of the hydrogen halides. The CTTS band provides a spectroscopically observable feature for the acidic dissociation. The calculated spectra were compared with our new experimental photodissociation data for larger water clusters doped with HCl and HBr. We conclude that HCl and HBr dissociate to a large extent on the surface of ice nanoparticles at temperatures near 120 K and photoactive products are formed. The acidic dissociation of HX leads to an enhancement by about 4 orders of magnitude of the HCl photolysis rate in the 200-300 nm region, which is potentially relevant for the halogen budget in the atmosphere.
Authors:
Milan Oncák; Petr Slavícek; Viktoriya Poterya; Michal Fárník; Udo Buck
Related Documents :
23567115 - One-step synthesis of agarose coated magnetic nanoparticles and their application in th...
21130615 - Comparison of n-tetradecane/electrolyte emulsions properties stabilized by dppc and dpp...
21361305 - Freezing transition and interaction potential in monolayers of microparticles at fluid ...
24736045 - Diversity of rare and abundant bacteria in surface waters of the southern adriatic sea.
21356595 - Responses to desiccation injury in developing wheat embryos from naturally- and artific...
18066485 - Relationship of geographic distance, depth, temperature, and viruses with prokaryotic c...
Publication Detail:
Type:  Journal Article     Date:  2008-05-29
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  112     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2008 Jun 
Date Detail:
Created Date:  2008-06-12     Completed Date:  2008-07-11     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  5344-53     Citation Subset:  -    
Affiliation:
Department of Physical Chemistry, Institute of Chemical Technology Prague,Technická 5, Prague 6, Czech Republic.
Export Citation:
APA/MLA Format     Download EndNote     Download BibTex
MeSH Terms
Descriptor/Qualifier:

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


Previous Document:  Molecular dynamics simulations of perylene and tetracene librations: comparison with femtosecond upc...
Next Document:  Synthesis and biological evaluation of D-amino acid oxidase inhibitors.