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master's thesis
Utjecaj otapala na Hammettove sigma konstante
Zagreb: University of Zagreb, Faculty of Science, 2019. urn:nbn:hr:217:599367
Kern, Matej
University of Zagreb
Faculty of Science
Department of Chemistry

Institutional repository: Repository of the Faculty of Science

Cite this document

Kern, M. (2019). Utjecaj otapala na Hammettove sigma konstante (Master's thesis). Zagreb: University of Zagreb, Faculty of Science. Retrieved from https://urn.nsk.hr/urn:nbn:hr:217:599367

Kern, Matej. "Utjecaj otapala na Hammettove sigma konstante." Master's thesis, University of Zagreb, Faculty of Science, 2019. https://urn.nsk.hr/urn:nbn:hr:217:599367

Kern, Matej. "Utjecaj otapala na Hammettove sigma konstante." Master's thesis, University of Zagreb, Faculty of Science, 2019. https://urn.nsk.hr/urn:nbn:hr:217:599367

Kern, M. (2019). 'Utjecaj otapala na Hammettove sigma konstante', Master's thesis, University of Zagreb, Faculty of Science, accessed 22 November 2024, https://urn.nsk.hr/urn:nbn:hr:217:599367

Kern M. Utjecaj otapala na Hammettove sigma konstante [Master's thesis]. Zagreb: University of Zagreb, Faculty of Science; 2019 [cited 2024 November 22] Available at: https://urn.nsk.hr/urn:nbn:hr:217:599367

M. Kern, "Utjecaj otapala na Hammettove sigma konstante", Master's thesis, University of Zagreb, Faculty of Science, Zagreb, 2019. Available at: https://urn.nsk.hr/urn:nbn:hr:217:599367

Metadata
TitleUtjecaj otapala na Hammettove sigma konstante
Title (english)Solvent effect on Hammett sigma constants
AuthorMatej Kern
MentorZlatko Mihalić (mentor)
Committee memberZlatko Mihalić (predsjednik povjerenstva)
Committee memberTomica Hrenar (član povjerenstva)
Committee memberNives Galić (član povjerenstva)
Committee memberIvan Kodrin (član povjerenstva)
GranterUniversity of Zagreb
Faculty of Science
(Department of Chemistry)
Zagreb
Defense date and country2019-09-30, Croatia
Scientific / art field,
discipline and subdiscipline		NATURAL SCIENCES
Chemistry
Abstract
Ispitan doprinos specifičnih interakcija DMSO-a prilikom računa Hammettovih sigma konstanti reakcije disocijacije para-supstituiranih benzojevih kiselina. Korištene su homodezmotske reakcije kako bi se izbjegao značajno zahtjevniji račun solvatacije protona u DMSO-u. Račun geometrija, slobodne energije solvatacije i termičkih korekcija obavljen je na PBE0/def2-TZVPD/SMD razini teonije dok su finalne energije računate na B2PLYPD3/ def2QZVPPD razini. Solvatacija je opisana kontinuumom te klaster-kontinuum metodom s do 3 molekule vode, odnosno jednom molekulom DMSO-a u klasteru. Valjanost metode potvrđena je usporedbom izračunatih pKa vrijednosti u vodi s literaturnima. Metoda se pokazala uspješnom u računu pKa vrijednosti u vodi uz upotrebu 2 ili 3 molekule vode u klasteru. Račun kontinuum solvatacijom u DMSO-u pokazao je izvrsno slaganje s literaturnim podacima. Klasteri s molekulom DMSO-a dali su lošije rezultate od samo kontinuum solvatacije uzrok čega bi trebalo istražiti.
Abstract (english)
The disociacion of para-benzoic acids in water and DMSO was investigated to estimate the contribution of specific solvent interactions in the calculation of Hammett σ constants. Homodesmic reactions were used to achieve the maximal cancelation of error caused by deficiencies at this level of theory. Calculation of geometries, standard Gibbs solvation energies and thermal corections was done at the PBE0/def2-TZVPD/SMD level, while single point energies were computed at the B2PLYP-D3/def2-QZVPPD level of theory. Solvation was modeled by continuum and cluster-continuum methods with up to three discrete molecules of water or one molecule of DMSO pressent in the clusters. Validation of the method was done by pKa calculation in water which was in good agreement with values taken from literature for clusters containing two or three molecules of water. Calculations in DMSO using continuum solvation showed agreement with literature as good as the best water clusters. DMSO clusters predicted worse results which merits further investigation.
Keywords
Keywords (english)
Languagecroatian
URN:NBNurn:nbn:hr:217:599367
Study programmeTitle: Graduate university studies in chemistry; specializations in: Research programme
Course: Research programme
Study programme type: university
Study level: graduate
Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
Type of resourceText
File originBorn digital
Access conditionsOpen access
Terms of useLicence In copyright icon
Created on2019-10-17 14:08:33