Browsing by Subject "wave-functions"
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Item Relativistic Ab initio Study On PtF and HePtF(2010-01) Zou, Wenli L.; Liu, Yang; Boggs, James E.; Zou, Wenli L.; Liu, Yang; Boggs, James E.The electronic structures and spectroscopic constants of the first three low-lying electronic states (Omega = 1/2, 3/2, and 5/2) of the linear HePtF complex were investigated by highly accurate relativistic ab initio methods, in which the spin-orbit coupling was taken into account, and compared with the results of PtF. It shows that the complex is significantly different from the typical van der Waals systems because of short He-Pt bond distances (1.80 similar to 1.87 angstrom), large He-Pt stretching frequencies (500 similar to 600 cm(-1)), considerable binding energies (1400 similar to 2500 cm(-1) with corrections), and a small electron transfer from helium (about 0.06). However, the topological analysis of the electron density distribution indicates that there is strong van der Waals interaction in the He-Pt bond instead of weak covalent one.Item Structural and Electronic Characterization of Multi-Electron Reduced Naphthalene (BIAN) Cobaloximes(2015-04) Williams, Owen M.; Cowley, Alan H.; Rose, Michael J.; Williams, Owen M.; Cowley, Alan H.; Rose, Michael J.Reported here are the syntheses and characterization of cobaloximes that feature a bis(imino) acenaphthene (BIAN) appended ligand. The X-ray crystal structures and spectroscopy (H-1 NMR or EPR) of the complexes within the series [Co(aqdBF(2))(2)(MeCN)(2)] (1), [Co(aqdBF(2))(MeCN)(2)](-) (2) and [Co(aqdBF(2))(2)-( MeCN)2](2-) (3, 3') are reported and the 3-electron reduced complex [Co(aqdBF(2))(2)(MeCN)(2)](3-) (4) has been prepared in situ and characterized by H-1 NMR spectroscopy. The X-ray crystal structures revealed the presence of a 6-coordinate Co-II species (1), a 5-coordinate Co-I species (2), and a 4-coordinate complex (3, 3'). In the case of complex 3, evidence from single crystal EPR spectroscopy (g(parallel to) = 2.017, g(perpendicular to) = 1.987; <10 G linewidths) in conjunction with DFT calculations indicate that the EPR signal originates from a delocalized ligand-based unpaired spin. The frontier orbitals obtained from DFT calculations on 1, 2, 3, & 4 support the electronic assignments that were observed spectroscopically. The cathodic cyclic voltammogram (CV) of the solvato congener in DMF solution, namely [Co(aqdBF(2))(2)(DMF)(2)], exhibits three reversible redox events near -1.0, -1.5 and -2.0 V vs. Fc/Fc(+). Catalytic proton reduction was observed by CV near the third redox peak. Compared with other cobaloximes (E-cat = -1.0 V), the delay of catalytic onset arises from the existence of a series of resonance-stabilized intermediates.