Usporedba DFT metoda za računanje elektrokemijskih parametara ferocenskih derivata

master's thesis

• Title (english): Comparison of DFT methods used in calculation of eledtrochemical parameters of ferrocene derivatives
• Author: Katarina Filipović
• Mentor: Valerije Vrček (mentor)
• Committee member: Davor Šakić (predsjednik povjerenstva)
• Committee member: Valerije Vrček (član povjerenstva)
• Committee member: Tin Weitner (član povjerenstva)
• Granter: University of Zagreb; Faculty of Pharmacy and Biochemistry; (Department of analytical chemistry); Zagreb
• Defense date and country: 2018-07-17, Croatia
• Scientific / art field, discipline and subdiscipline: BIOMEDICINE AND HEALTHCARE; Pharmacy; Pharmacy

Abstract

Ferocen i njegovi derivati posjeduju korisna fizikalno-kemijska svojstva (npr. obojanost, termička
stabilnost, jedno-elektronska redukcija), te se primjenjuju u znanosti o materijalima, a njihova
primjena u biomedicini intenzivno se istražuje u posljednjim desetljećima. Znajući da su
elektrokemijska svojstva ferocenskih derivata u korelaciji s njihovom biološkom aktivnosti,
proučavanje ovih svojstava od iznimne je važnosti. Primjena računalne kemije u predviđanju
elektrokemijskih svojstava ferocenskih derivata može usmjeriti složene eksperimentalne
procedure, te ubrzati pronalazak odgovarajućeg derivata. Za izračun ferocenskih derivata često su
korištene računalne metode koje se koriste teorijom funkcionala gustoće (DFT). U ovom se radu
proučava uspješnost predviđanja elektrokemijskog potencijala korištenjem pojedinih DFT
funkcionala i ispituje utjecaj Hartree-Fock (HF) izmjene u različitim funkcionalima usporedbom s
literaturnim eksperimentalnim redoks potencijalima za 16 ferocenskih derivata određenih u
tetrahidrofuranu kao otapalu. Becke funkcionali bez HF izmjene (B-LYP 0%) daju lošije procjene
od funkcionala s većim udjelom HF izmjene (B3-LYP 25% i B-HandH-LYP 50%), ali za razliku
od B3-LYP i B-HandH-LYP kod B-LYP nema velikih odstupanja (> 200 mV) kod određenih
spojeva. Minnesotta funkcionali (M06-L, M06 i M06-2X) pokazuju sličan trend, pri čemu M06 i
M06-2X imaju odličnu korelaciju, ali i nemogućnost izračuna nekih ferocenskih derivata.

Abstract (english)

Ferrocene and its derivatives have useful physical and chemical properties (e.g. coloration, thermal
stability, one-electron reduction) and are used in material science. Biomedical application of
ferrocene derivatives has been investigated intensively over the past decades. Correlation of
ferrocene derivatives electrochemical properties with their respective biological activity, became a
strong reason to study those properties. Use of computational chemistry for the prediction of
electrochemical properties of ferrocene derivatives can steer complex experimental procedures and
accelerate the discovery of derivatives with desired properties. Computational methods employing
Density Functional Theory (DFT) are often used in the calculation of ferrocene derivatives. In this
work, the efficacy of the prediction of electrochemical potential using different DFT functionals is
studied. Moreover, the influence of Hartree-Fock (HF) exchange in different functionals is
examined. This is achieved by comparing literature experimental data of redox potentials for 16
ferrocene derivatives, whose potentials were obtained in tetrahydrofuran, with calculated potentials.
Becke functionals that don’t contain HF exchange (B-LYP 0%) allow poorer estimates than
functionals with a higher proportion of HF exchange (B3-LYP 25% and B-HandH-LYP 50%). The
advantage is that B-LYP, unlike B3-LYP and B-HandH-LYP, doesn’t show large deviations (>200
mV) for certain compounds. Minnesotta functionals (M06-L, M06 and M06-2X) follow a similar
trend, whereby M06 and M06-2X have a high correlation, but at the same time, for some of
ferrocene derivatives calculations fail at those levels of theory.

• Keywords: ferocen; teorija funkcionala gustoće (DFT); redoks potencijal
• Keywords (english): ferrocene; density Functional Theory (DFT); redox potentials
• Language: croatian
• URN:NBN: urn:nbn:hr:163:848678
• Study programme: Title: Pharmacy; Study programme type: university; Study level: integrated undergraduate and graduate; Academic / professional title: magistar/magistra farmacije (magistar/magistra farmacije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access
• Created on: 2018-12-03 14:03:34