Craig A. Bayse

Department of Chemistry and Biochemistry

www.gaussian.com

Electronic structure software package

Introduced by Nobel Laureate John Pople in 1970

Approximate solutions to Schrödinger’s Equation

H = E

Applications:

◦ Optimizing geometries of chemical structures

◦ Calculating chemical properties (IR, NMR, UV/Vis, etc)

◦ Modeling reaction mechanisms

What do you need to run a G09 job?◦ Structure

◦ Basis set – represents the wavefunction

◦ Method – represents the Hamiltonian

Inexpensive, but inaccurate (MM, semiempirical)

Expensive, state-of-the-art (CCSD(T))

Balanced (DFT, current favorite)

Wide range of functionals available

Fast on multiprocessor execution

GaussView - GUI

Lewisite/British Anti-Lewisite

L.K. Harper, S. Antony and C.A. Bayse. ‘Thiol reduction of arsenite and selenite: DFT modeling of the pathways to an As-Se bond.’ Chemical Research in Toxicology. Submitted.

C.A. Bayse, L.K. Harper, J.L. Ming and R.D. Pike. ‘The effect of amine and phosphine decoration on the photoluminescence of 1-D copper(I) and silver(I) cyanide coordination polymers.’ (invited) Dalton Transations. 43 (2014) 11243-11251.

F. Li, P.B. Lutz, Y. Pepelyayeva, E.S.J. Arnér, C.A. Bayse and S. Rozovsky. ‘Conformational dynamics of redox active motifs in selenoproteins.’ Proceedings of the National Academy of Sciences. 111 (2014) 6976-6981.

S. Antony and C.A. Bayse. ‘Density functional theory study of the attack of ebselen on a zinc finger model.’ Inorganic Chemistry. 52 (2013) 13803-13805.

C.A. Bayse and K.N. Ortwine. ‘Modeling the glutathione peroxidase-like activity of a cyclic seleninate by DFT and solvent-assisted proton exchange.’ European Journal of Inorganic Chemistry. (2013) 3680-3688.

P.B. Lutz and C.A. Bayse. ‘Orbital-based insights into parallel-displaced and twisted conformations in - interactions.’ Physical Chemistry Chemical Physics. 15 (2013) 9397-9406.

P.O. Atolagbe, K.N. Taylor, S.E. Wood, A.L. Rheingold, L.K. Harper, C.A. Bayse and T.J. Brunker. ‘Ruthenium(II) dichloride complexes of chiral, tetradentateaminosulfoxide ligands: Stereoisomerism and redox-induced linkage isomerism.’ Inorganic Chemistry. 52 (2013) 1170-1172.

J.P. Safko, J.E. Kuperstock, S.M. McCullough, A.M. Noviello, X. Li, J.P. Killarny, C. Murphy, H.H. Patterson, C.A. Bayse and P.D. Pike. ‘Network formation and photoluminescence in copper(I) halide complexes with substituted piperazineligands.’ Dalton Transactions. 41 (2012) 11663-11674.

S. Antony and C.A. Bayse. ‘Modeling the mechanism of the glutathione peroxidase mimic ebselen.’ Inorganic Chemistry. 50 (2011) 12075-12084.

C.A. Bayse and A. Pavlou. ‘The relationship between Se···N,O bond strength and the activity of glutathione peroxidase mimics: A DFT study incorporating solvent-assisted proton exchange (SAPE).’ Organic & Biomolecular Chemistry. 9(2011) 8006-8015.

C.A. Bayse, J.L. Ming, K.M. Miller, S.M. McCollough and R.D. Pike. ‘Photoluminescence of silver(I) and gold(I) cyanide 1D coordination polymers.’ Inorganica Chimica Acta. 375 (2011) 47-52.

Important non-bonding interaction◦ Petroleum science, nanotubes

◦ Biochemical recognition

◦ Crystal packing

We are developing new models

Turing allows us to handle larger systems

42 e150 bf 156 e

528 bf 270 e906 bf

374 e2448 bf

Healthy thyroid function requires Iodine andselenium!

Mechanism known, but how does it occur?◦ Protein structure was unknown until recently

Important to treat thyroid illnesses

Our novel mechanism modeledwith G09 with small models

Verified in prestige journals (JACS and PNAS)

Scale up with Turing!

Pre-Turing Turing And Beyond…

Pigments extracted from Stentor are photosensitive and potential photodynamic therapy agents

Compounds are difficult to characterize

Simulation of the UV/Vis spectrum using

TD-DFT

Model mechanisms

Images from eol.org