Benchmarking Semiempirical Methods To Compute Electrochemical Formal Potentials

Gieseking, Rebecca L. M.; Ratner, Mark A.; Schatz, George C.

doi:10.1021/acs.jpca.8b05143

Title: Benchmarking Semiempirical Methods To Compute Electrochemical Formal Potentials

Journal Article · Thu Jul 19 00:00:00 EDT 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b05143· OSTI ID:1464278

^[1]; Ratner, Mark A. ^[1];

^[1]

Department of Chemistry, Northwestern University 2145 Sheridan Road, Evanston, Illinois 60208, United States

Computational methods to predict and tune electrochemical redox potentials are important for the development of energy technologies. Here, we benchmark several semiempirical models to compute reduction potentials of organic molecules, comparing approaches based on (1) energy differences between the S₀ and one-electron-reduced D₀ states of the isolated molecules and (2) an orbital energy shift approach based on tuning the charge-transfer triplet energy of the Ag₂₀-molecule complex; the second model enables explicit modeling of electrode–molecule interactions. For molecules in solution, the two models yield nearly identical results. Both PM7 and PM6 predict formal potentials with only a slight loss of accuracy compared to standard density functional theory models, and the results are robust across several choices of geometries and implicit solvent models. PM6 and PM7 show dramatically improved accuracy over older semiempirical Hamiltonians (MNDO, AM1, PM3, and INDO/S). However, our recently developed INDO parameters model the electronic properties of our Ag₂₀ model electrode much more accurately than does PM7. These results demonstrate the need for further development of semiempirical models to accurately model molecules on surfaces.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0004752

OSTI ID:: 1464278

Alternate ID(s):: OSTI ID: 1508603

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Vol. 122 Journal Issue: 33; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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