Show simple item record

dc.contributor.supervisor Schreckenbach, Georg (Chemistry) en_US
dc.contributor.author Afaneh, Akef
dc.date.accessioned 2015-08-11T17:11:20Z
dc.date.available 2015-08-11T17:11:20Z
dc.date.issued 2012-03 en_US
dc.date.issued 2014-06 en_US
dc.date.issued 2014-07 en_US
dc.date.issued 2015-06 en_US
dc.identifier.citation Harvard en_US
dc.identifier.citation Vancouver en_US
dc.identifier.citation ACS Style en_US
dc.identifier.citation ACS Style en_US
dc.identifier.uri http://hdl.handle.net/1993/30661
dc.description.abstract This thesis presents the basic concepts of electronic structure theory and the chemical properties of mercury. The theoretical foundation of DFT and the consequences of relativity are also introduced. The electronic structure of Hg(II) ions, [Hg(L)n(H2O)m]q (L = HO-, Cl-, HS-, S2-) has been studied. We show, in this thesis, that the charge transfer (that is calculated from the hard-soft-acid-base principle (Pearson’s principle)), the total NBO charge and the interaction energies are strongly correlated. Our studies indicate the effect of the solvent on the global electrophilicity, the charge transfer and consequently the interaction strength between Hg(II) and ligand L. The formation constants, logK, of Hg2+−complexes are calculated. The procedure that we follow in this thesis to calculate the formation constants, logK’s, are in good agreement with the extrapolated experimental values. We introduce and explain why it is important adding water molecules explicitly during the calculations of the logK. The recommended logK value of HgS is 27.2. We examined two different types of organic compounds as sensors for heavy metal ions: lumazine (Lm) and 6-thienyllumazine (TLm). We found that the simple calculation of pKa values using DFT methods and implicit solvent models failed to reproduce the experimental values. However, calculated orbital energies and gas phase acidities both indicate that the compound TLm is inherently more acidic than the parent species Lm. We demonstrate that: (1) we need to take in our consideration the population of each tautomer and conformer during the calculations of the pKa values, and (2) thienyl group has indirect effect on the acidity of the proton on N1 in the uracil ring. Last but not least, the fluorescence spectrum of the sensors (L) and their [(L)nM(H2O)m]2+ complexes (L = Lumazine (Lm) and 6-thienyllumazine (TLm) and M = Cd2+and Hg2+) are calculated using time dependent DFT (TDDFT). The results show that TDDFT is in good agreement with experimental results. This chapter provides a new concept in the design of fluorescence turn-on/off sensors that has wider applicability for other systems. Finally, we provide a summary of the works compiled in this thesis and an outlook on potential future work. en_US
dc.publisher Springer International Publishing AG en_US
dc.publisher Wiley en_US
dc.publisher American Chemical Society en_US
dc.publisher American Chemical Society en_US
dc.rights info:eu-repo/semantics/openAccess
dc.subject Computational chemistry, Molecular modelling, Density functional theory (DFT), Mercury complexes, Hard-soft acid base principle (HSAB), Formation constant, Metal orbital control en_US
dc.title Computational investigations of the electronic structure of molecular mercury compounds: ion-selective sensors en_US
dc.type info:eu-repo/semantics/doctoralThesis
dc.degree.discipline Chemistry en_US
dc.contributor.examiningcommittee Budzelaar, Peter (Chemistry) Whitmore, Mark (Physics and Astronomy) Wang, Feiyue (Environment and Geography) Wetmore, Stacey (Chemistry and Biochemistry, University of Lethbridge) en_US
dc.degree.level Doctor of Philosophy (Ph.D.) en_US
dc.description.note October 2015 en_US


Files in this item

This item appears in the following Collection(s)

Show simple item record

View Statistics