Goodpaster Research Group |

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We focus on the development and application of new electronic structure theories. Specifically, we are interested in multi-scale models, which allow for the study of large and extended systems. We are developing quantum-embedding theories, which treat different regions of the system at different levels of accuracy. This allows for a high chemical accuracy in a small region, such as an active site of a catalyst, and a less accurate, but more computationally efficient description of the remainder. These tools can then be used to perform first-principle studies on large, reactive, and condensed phase systems. We are interested in applying these methods to metalloenzymes, heterogeneous catalysts, and metal-organic frameworks.

Recent Publications and News Items

Plasmon-Driven C–N Bond Cleavage Across a Series of Viologen Derivatives

Here, we investigate the nature of plasmon-driven reactions on three viologen derivatives: methyl viologen, ethyl viologen, and benzyl viologen. Viologens have traditionally been employed as excellent redox agents due to their ability to reversibly stabilize additional electrons in their molecular structures. However, by using surface-enhanced Raman spectroscopy, we were able to directly observe a C–N bond cleavage on benzyl and ethyl viologen to form 4,4′-bipyridine on the surface of gold film-over-nanosphere substrates.

Brooks, J.L.; Chulhai, D.V.; Yu, Z.; Goodpaster, J.D.; Frontiera, R.R. J. Phys. Chem. C 2019, 123, 48, 29306-29313

http://dx.doi.org/10.1021/acs.jpcc.9b08179

Plasmon reaction mechanism and Raman spectrum

Carbodiimide Synthesis via Ti-Catalyzed Nitrene Transfer from Diazenes to Isocyanides

Simple Ti imido halide complexes such as [Br2Ti(NtBu)py2]2 are competent catalysts for the synthesis of unsymmetrical carbodiimides via Ti-catalyzed nitrene transfer from diazenes or azides to isocyanides. Both alkyl and aryl isocyanides are compatible with the reaction conditions, although product inhibition with sterically unencumbered substrates sometimes limits the yield when diazenes are employed as the oxidant. The reaction mechanism has been investigated both experimentally and computationally, wherein a key feature is that the product release is triggered by electron transfer from an η2-carbodiimide to a Ti-bound azobenzene.

Beaumier, E.P.; McGreal, M.E; Pancoast, A. R.; Wilson, H.; Moore, J. T.; Graziano, B. J.; Goodpaster, J. D.; Tonks, I.A; ACS Catalysis, 2019, 9, 12, 11753-11762

http://dx.doi.org/10.1021/acscatal.9b04107

Absolutely Localized Projection-Based Embedding for Excited States

A quantum embedding method that allows for the calculation of local excited states embedded in a Kohn-Sham density functional theory (DFT) environment. Projection-based quantum embedding methodologies provide a rigorous framework for performing DFT-in-DFT and wave function in DFT (WF-in-DFT) calculations. The use of absolute localization, where the density of each subsystem is expanded in only the basis functions associated with the atoms of that subsystem, provide improved computationally efficiency for WF-in-DFT calculations by reducing the number of orbitals in the WF calculation.

Wen, X.; Graham, D.S.; Chulhai, D. V.; Goodpaster, J. D.; Journal of Chemical Theory and Computation, 2019, Just Accepted.

http://dx.doi.org/10.1021/acs.jctc.9b00959

The Stability of the Complex and the Basicity of the Anion Impact the Selectivity and Affinity of Tripodal Gadolinium Complexes for Anions

The affinities and selectivities of lanthanide complexes with open coordination sites for anions vary considerably with the chelate. In order to determine the effect of the stability of a lanthanide complex on its affinity for anions, five different complexes featuring different bidentate chelating moieties were synthesized, and their affinity for anions in water at neutral pH were evaluated by longitudinal relaxometry measurements.

Ramakrishnam Raju, M. V.; Wilharm, R. K.; Dresel, M. J.; McGreal, M. E.; Mansergh, J. P.; Marting, S. T.; Goodpaster, J. D.; Pierre, V. C. Inorganic Chemistry Article 2019, 58, 22, 15189-15201

http://dx.doi.org/10.1021/acs.inorgchem.9b02133

Fully Quantum Embedding with Density Functional Theory for Full Configuration Interaction Quantum Monte Carlo

We develop a fully quantum embedded version of initiator full configuration interaction quantum Monte Carlo (i–FCIQMC) and apply it to study an ionic bond (lithium hydride, LiH) and a covalent bond (hydrogen flouride, HF) physisorbed to a benzene molecule. The embedding is performed using a recently developed Huzinaga projection operator approach, which affords good synergy with i–FCIQMC by minimizing the number of orbitals in the calculation.

Petras, H. R.; Graham, D. S.; Ramadugu, S. K.; Goodpaster, J. D.; Shepherd, J. J. Journal of Chemical Theory and Computation 2019 15 (10), 5332-5342

http://dx.doi.org/10.1021/acs.jctc.9b00571

Embedded i-FCIQMC results of lithium benzene show good convergence with embedding.

On the Mechanism of Ti-Catalyzed Oxidative Nitrene Transfer in [2+2+1] Pyrrole Synthesis from Alkynes and Azobenzen

A combined computational and experimental study on the mechanism of Ti-catalyzed formal [2 + 2 + 1] pyrrole synthesis from alkynes and aryl diazenes is reported. This reaction proceeds through a formally TiII/TiIV redox catalytic cycle as determined by natural bond orbital (NBO) and intrinsic bond orbital (IBO) analysis. Kinetic analysis of the reaction of internal alkynes with azobenzene reveals a complex equilibrium involving Ti═NPh monomer/dimer equilibrium and Ti═NPh + alkyne [2 + 2] cycloaddition equilibrium along with azobenzene and pyridine inhibition equilibria prior to rate-determining second alkyne insertion.

Zachary W Davis-Gilbert, Xuelan Wen, Jason D. Goodpaster, and Ian A. Tonks, "On the Mechanism of Ti-Catalyzed Oxidative Nitrene Transfer in [2+2+1] Pyrrole Synthesis from Alkynes and Azobenzene", J. Am. Chem. Soc. 2018, 140, 23, 7267-7281

https://pubs.acs.org/doi/10.1021/jacs.8b03546

Projection-Based Correlated Wave Function in Density Functional Theory Embedding for Periodic Systems

We present a level shift projection operator-based embedding method for systems with periodic boundary conditions—where the “active” subsystem can be described using either density functional theory (DFT) or correlated wave function (WF) methods and the “environment” is described using DFT.

Dhabih, C.V.; Goodpaster, J.D. J. Chem. Theory Comput., 2018, 14, 4, 1928-1942

http://dx.doi.org/10.1021/acs.jctc.7b01154

Localized Level-Shift Wave Function in DFT Embedding

Huzinaga level-shift projection operator based DFT embedding

Chulhai, D.V.; Goodpaster, J.D. J. Chem. Theory Comput., 2017, 13(4), 1503–1508.

https://pubs.acs.org/doi/abs/10.1021/acs.jctc.7b00034

Breaking the Correlation between Energy Costs and Kinetic Barriers in Hydrogen Evolution via a Cobalt Pyridine-Diimine-Dioxime Catalyst

P. Huo, C. Uyeda, J. D. Goodpaster, J. C. Peters, T. F. Miller III, ACS Catal., 6, 6114-6123 (2016).

http://dx.doi.org/

Accurate and systematically improvable density functional theory embedding for correlated wavefunctions

J. D. Goodpaster, T. A. Barnes, F. R. Manby, and T. F. Miller III, J. Chem. Phys., 140, 18A507 (2014)

http://dx.doi.org/10.1063/1.4864040