Computational and experimental study of the structure, binding preferences, and spectroscopy of nickel(II) and vanadyl porphyrins in petroleum

The Journal of Physical Chemistry. B
Stanislav R StoyanovAndriy Kovalenko

Abstract

We present a computational exploration of five- and six-coordinate Ni(II) and vanadyl porphyrins, including prediction of UV-vis spectroscopic behavior and metalloporphyrin structure as well as determination of a binding energy threshold between strongly bound complexes that have been isolated as single crystals and weakly bound ones that we detect by visible absorption spectroscopy. The excited states are calculated using the tandem of the time-dependent density functional theory (TD-DFT) and the conductor-like polarizable continuum model (CPCM). The excited-state energies in chloroform solvent obtained by using two density functionals are found to correlate linearly with the experimental Soret and alpha-band energies for a known series of five-coordinate vanadyl porphyrins. The established linear correction allows simulation of the excited states for labile octahedral vanadyl porphyrins that have not been isolated and yields Soret and alpha-band bathochromic shifts that are in agreement with our UV-vis spectroscopic results. The PBE0 and PW91 functionals in combination with DNP basis set perform best for both structure and binding energy prediction. The reactivity preferences of Ni(II) and vanadyl porphyrins toward aromatic f...Continue Reading

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Citations

Feb 1, 2012·Computational & Theoretical Chemistry·Jenna Barbee, Aleksey E Kuznetsov
Sep 16, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·D Paul RillemaVenugopal KomReddy
May 8, 2013·Journal of Environmental Science and Health. Part A, Toxic/hazardous Substances & Environmental Engineering·J V HeadleyF J Wrona
Aug 20, 2020·Journal of Chemical Information and Modeling·Masoumeh Mousavi, Elham H Fini

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