Title
Exploring the limits of cryospectroscopy : least-squares based approaches for analyzing the self-association of HCl Exploring the limits of cryospectroscopy : least-squares based approaches for analyzing the self-association of HCl
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Oxford ,
Subject
Chemistry
Source (journal)
Spectrochimica acta: part A: molecular and biomolecular spectroscopy. - Oxford
Volume/pages
154(2016) , p. 89-97
ISSN
1386-1425
ISI
000366071200014
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
To rationalize the concentration dependent behavior observed for a large spectral data set of HCl recorded in liquid argon, least-squares based numerical methods are developed and validated. In these methods, for each wavenumber a polynomial is used to mimic the relation between monomer concentrations and measured absorbances. Least-squares fitting of higher degree polynomials tends to overfit and thus leads to compensation effects where a contribution due to one species is compensated for by a negative contribution of another. The compensation effects are corrected for by carefully analyzing, using AIC and BIC information criteria, the differences observed between consecutive fittings when the degree of the polynomial model is systematically increased, and by introducing constraints prohibiting negative absorbances to occur for the monomer or for one of the oligomers. The method developed should allow other, more complicated self-associating systems to be analyzed with a much higher accuracy than before.
Full text (open access)
https://repository.uantwerpen.be/docman/irua/9a37bb/128584.pdf
E-info
https://repository.uantwerpen.be/docman/iruaauth/8626ec/128584.pdf
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000366071200014&DestLinkType=RelatedRecords&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000366071200014&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000366071200014&DestLinkType=CitingArticles&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
Handle