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  1. N-Heterocyclic carbenes (NHCs) are widely used ligands in transition metal catalysis. Notably, they are increasingly encountered in heterogeneous systems. While a detailed knowledge of the possibly multiple metal environments would be essential to understand the activity of metal-NHC-based heterogeneous catalysts, only a few techniques currently have the ability to describe with atomic-resolution structures dispersed on a solid support. Here, we introduce a new dynamic nuclear polarization (DNP) surface-enhanced solid-state nuclear magnetic resonance (NMR) approach that, in combination with advanced density functional theory (DFT) calculations, allows the structure characterization of isolated silica-supported Pt-NHC sites. Notably, we demonstrate that the signal amplification provided by DNP in combination with fast magic angle spinning enables the implementation of sensitive 13C-195Pt correlation experiments. By exploiting 1J(13C-195Pt) couplings, 2D NMR spectra were acquired, revealing two types of Pt sites. For each of them, 1J(13C-195Pt) value was determined as well as 195Pt chemical shift tensor parameters. To interpret the NMR data, DFT calculations were performed on an extensive library of molecular Pt-NHC complexes. While one surface site was identified as a bis-NHC compound, the second site most likely contains a bidentate 1,5-cyclooctadiene ligand, pointing to various parallel grafting mechanisms. The methodology described here represents a new step forward in the atomic-level description of catalytically relevant surface metal-NHC complexes. In particular, it opens up innovative avenues for exploiting the spectral signature of platinum, one of the most widely used transition metals in catalysis, but whose use for solid-state NMR remains difficult. Our results also highlight the sensitivity of 195Pt NMR parameters to slight structural changes. 
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  2. Abstract

    The Walker circulation connects the regions with deep atmospheric convection in the western tropical Pacific to the shallow‐convection, tropospheric subsidence, and stratocumulus cloud decks of the eastern Pacific. The purpose of this study is to better understand the multi‐scale interactions between the Walker circulation, cloud systems, and interactive radiation. To do this we simulate a mock‐Walker Circulation with a full‐physics general circulation model using idealized boundary conditions. Our experiments use a doubly‐periodic domain with grid‐spacing of 1, 2, 25, and 100 km. We thus span the range from General Circulation Models (GCMs) to Cloud‐system Resolving Models (CRMs). Our model is derived from the Geophysical Fluid Dynamics Laboratory atmospheric GCM (AM4.0). We find substantial differences in the mock‐Walker circulation simulated by our GCM‐like and CRM‐like experiments. The CRM‐like experiments have more upper level clouds, stronger overturning circulations, and less precipitation. The GCM‐like experiments have a low‐level cloud fraction that is up to 20% larger. These differences leads to opposite atmospheric responses to changes in the longwave cloud radiative effect (LWCRE). Active LWCRE leads to increased precipitation for our GCMs, but decreased precipitation for our CRMs. The LWCRE leads to a narrower rising branch of the circulation and substantially increases the fraction of precipitation from the large‐scale cloud parameterization. This work demonstrates that a mock‐Walker circulation is a useful generalization of radiative convective equilibrium that includes a large‐scale circulation.

     
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  3. Abstract

    Global tropical cyclone (TC) frequency is investigated in a 50‐km‐resolution aquaplanet model forced by zonally symmetric sea surface temperature (SST). TC frequency per unit area is found to be proportional to the Coriolis parameter at the intertropical convergence zone (ITCZ), as defined by the latitude of maximum precipitation. As the latitude of maximum SST is shifted northward from the equator, the precipitation maximum moves northward and TC frequency increases. When the SST maximum is shifted northward past 25°N, the precipitation maximum remains between 15°N and 20°N, and TC frequency per unit area is approximately constant. When applied to observed precipitation and SST data, the same scaling captures a substantial fraction of observed TCs. Results suggest that future changes in TC activity will be modulated by changes in the large‐scale circulation, and in particular that the ITCZ location is an important determinant of the number of TCs.

     
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