title: Theoretical prediction of structural, vibrational and NMR parameters of plastic optical fiber (POF) material precursors. Cis and trans perhydro- and perfluoro-2-methylene-4,5-dimethyl-1,3-dioxolanes.
abstract: Density functional theory (DFT) prediction of cis and trans perhydro- and perfluoro-2-methylene-4,5-dimethyl-1,3-dioxolanes structure, supported by vibrational analysis and calculation of multinuclear isotropic nuclear magnetic resonance (NMR) shieldings and indirect spin-spin couplings (SSCCs) was performed. The performance of the used methodology was verified on 1,3-dioxolane selected as model compound. The structures of hydrogenated and fluorinated monomers of POF materials were calculated using B3LYP and BLYP density functionals combined with 6-311++G(3df,2pd) basis set. The BLYP/6-311++G(3df,2pd) level of theory was suggested for vibrational analysis. Gauge independent atomic orbitals (GIAO) calculations were applied to distinguish between cis and trans isomers of the title 1,3-dioxolanes. For obtaining both accurate nuclear shieldings and individual spin-spin coupling constants the BHandH/aug-pcJ-2 level of theory was chosen. The protocol used for the calculations nicely showed remarkable differences in vibrational spectra and NMR parameters of cis and trans isomers of the studied 1,3-dioxolane derivatives before and after fluorination.
authors.affiliation: Department of Physics, 4513 Manhattan College Parkway Riverdale, New York 10471, USA. Electronic address: farhod.nozirov@gmail.com.
authors.forename: Farhod
authors.initials: F
authors.lastname: Nozirov
authors.affiliation: Faculty of Chemistry, Opole University, 48, Oleska Street, 45-052 Opole, Poland. Electronic address: teobaldk@gmail.com.
authors.forename: Teobald
authors.initials: T
authors.lastname: Kupka
authors.affiliation: Faculty of Chemistry, Opole University, 48, Oleska Street, 45-052 Opole, Poland.
authors.forename: Michał
authors.initials: M
authors.lastname: Stachów
mesh_terms: D004148:Dioxolanes / Q000737:chemistry*; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D055100:Optical Fibers; D010969:Plastics / Q000737:chemistry*; D011789:Quantum Theory; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D014732:Vibration
chemical_list: D004148:Dioxolanes; D010969:Plastics
keywords: DFT; GIAO NMR; POF; Perfluoro-2-methylene-4,5-dimethyl-1,3-dioxolane