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dc.contributor.author
Wolcan, Ezequiel
dc.date.available
2016-04-08T15:48:02Z
dc.date.issued
2014-04
dc.identifier.citation
Wolcan, Ezequiel; On the origins of the absorption spectroscopy of pterin and Re(CO)3(pterin)(H2O) aqueous solutions. A combined theoretical and experimental study; Elsevier; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 129; 4-2014; 173-183
dc.identifier.issn
1386-1425
dc.identifier.uri
http://hdl.handle.net/11336/5083
dc.description.abstract
The origins of the absorption spectroscopy of pterin and Re(CO)3(pterin)(H2O) complex as a function of pH is studied using the hybrid functional B3LYP and PBE0 in combination with 6-311++G(d,p) and LanL2TZ(f) basis sets. A natural bond analysis was performed to the principal molecular orbitals involved in the electronic transitions of the studied compounds. The low energy band of pterin, which is described as a H→L electronic transition, can be interpreted as an admixture of π→π(*), n→π(*) and n→n electronic transitions involving π(C2-N1, C6-N5, C9-C10) and n(C2) orbitals of the HOMO and π(*)(C6-N5, C7-N8) and n(C4) orbitals of the LUMO. The low energy band of Re(CO)3(pterin)(H2O) can be described as a combination of different MLLCT transitions where electron density residing on different π orbitals of carbonyl-Re bonds and lone pairs of Re is transferred to pterin moiety. Besides MLLCT transitions, IL, LLCT and LLMCT transitions contribute the absorptions of the Re(I) complex in the wavelength region corresponding to the high energy bands. The calculated electronic spectra of the acid and base forms of pterin and Re(CO)3(pterin)(H2O) were simulated from the theoretical results and compared to the experimental absorption spectra with great accuracy both in position and relative intensities of the absorption bands.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Elsevier
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.subject
Pterin
dc.subject
Re(I) Tricarbonyl-Complex
dc.subject
Uv-Vis Spectroscopy
dc.subject
Acid-Base
dc.subject.classification
Físico-Química, Ciencia de los Polímeros, Electroquímica
dc.subject.classification
Ciencias Químicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
On the origins of the absorption spectroscopy of pterin and Re(CO)3(pterin)(H2O) aqueous solutions. A combined theoretical and experimental study
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2016-05-06 15:52:43.262787-03
dc.journal.volume
129
dc.journal.pagination
173-183
dc.journal.pais
Países Bajos
dc.journal.ciudad
Amsterdam
dc.description.fil
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de la Plata; Argentina
dc.journal.title
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/pmid/24727177
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2014.03.022
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1386142514004338
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1016/j.saa.2014.03.022


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