The Goldsmith Lab performs interdisciplinary research using state-of-the-art electronic-structure theory and molecular simulation, as well as data analytics tools,
to understand catalysts and materials under realistic conditions, and to help generate a platform for their design and use in sustainable chemical synthesis, alternative energy, and pollution reduction.
See the posters below for more information about our current research thrusts and research highlights.
Ab initio modeling of catalysts and materials
Click the poster below for some information about our research group thrusts, namely: (i) The computational investigation of amorphous and disordered materials for their use as catalysts and catalyst supports for alternative fuel production and pollution reduction;
(ii) Understanding of nanoclusters and atomically dispersed metal-complexes supported by metal oxides for natural gas conversion;
(iii) Homogeneous organometallic catalysis for specialty chemical production, especially for C-H activation of small molecules; and (iv) Using data analytics/machine learning/data mining tools to accelerate discovery of catalysts and materials.
Data analytics to discover materials-science insights
As part of the Novel Materials Discovery Laboratory, a major goal is to develop data analytics tools to uncover scientific insights from large materials repositories. While at the FHI Theory Department, Dr. Goldsmith applied subgroup discovery to find and describe interesting local patterns in materials-science data.
In collaboration with Dr. Boley, two illustrative examples were considered to: (1) discover interpretable models that classify the octet binary materials as either zincblende or rocksalt, and (2) elucidate structure-property relationships of gold clusters in the gas phase. Read here and here.
Understanding gold clusters in the gas phase
With the L. M. Ghiringhelli Group, we are examining the (meta)stable structures of gold clusters present at finite temperature using van der Waals (vdW) corrected density-functional theory and replica-exchange ab initio molecular dynamics. Inclusion of many-body vdW interactions is needed for predicting accurate isomer energetics, and its importance grows as the cluster size increases. Temperature effects are observed to typically stabilize three-dimensional structures over planar structures at finite temperature.
Gold cluster structures are assigned using far-IR spectroscopy obtained by the Fieleke Group and theoretical predictions.
Modeling isolated catalyst sites on amorphous supports
Modeling isolated sites on amorphous catalyst supports remains a major challenge. Typical strategies use cluster models with arbitrarily chosen constraints to model the rigid solid which impart arbitrary properties to the site. Alternatively no constraints are used, which results in sites with unrealistic flexibility. During Dr. Goldsmith's PhD studies in the Peters Group, they developed a systematic ab initio method to model isolated active sites on insulating amorphous
supports using small cluster models. The goal is to use the algorithm to facilitate the testing of catalytic mechanistic hypotheses. Read article here.
Water-catalyzed activation of H2O2 by methyltrioxorhenium
In collaboration with Susannah L. Scott's Group, we conducted a joint computational-experimental study of the reaction of CH3ReO3 (MTO) with H2O2 to understand the origins of large discrepancies
in previously reported experimental reaction kinetics and thermodynamics compared with computational results. We also explored MTO-catalyzed olefin epoxidation by H2O2, as it shows strong water acceleration effects, even though no step in the catalytic cycle explicitly consumes water.
The main cause of the observed acceleration is the water-dependence of the rates at which the active species are regenerated. Read here and here.
CO and NO-induced nanoparticle disintegration
Reactant-induced structural changes of supported metal nanoparticles (NPs) have been widely reported during heterogeneous catalysis. One common structural change is the reactant-induced disintegration of supported NPs, which can lead to catalyst deactivation or be employed as an effective way to achieve catalyst redispersion.
In collaboration with the Wei-Xue Li Group, we conducted an ab initio thermodynamics study to understand the effects of CO and NO reactants on the disintegration of
metal-oxide supported Rh, Pd, and Pt NPs into adatom-reactant complexes. Read article here.