Density functional theory and CCSD(T) evaluation of ionization potentials, redox potentials, and bond energies related to zirconocene polymerization catalysts.

Quantum-mechanical-based computational design of molecular catalysts requires accurate and fast electronic structure calculations to determine and predict properties of transition-metal complexes. For Zr-based molecular complexes related to polyethylene catalysis, previous evaluation of density functional theory (DFT) and wavefunction methods only examined oxides and halides or select reaction barrier heights. In this work, we evaluate the performance of DFT against experimental redox potentials and bond dissociation enthalpies (BDEs) for zirconocene complexes directly relevant to ethylene polymerization catalysis. We also examined the ability of DFT to compute the fourth atomic ionization potential of zirconium and the effect the basis set selection has on the ionization potential computed with CCSD(T). Generally, the atomic ionization potential and redox potentials are very well reproduced by DFT, but we discovered relatively large deviations of DFT-calculated BDEs compared to experiment. However, evaluation of BDEs with CCSD(T) suggests that experimental values should be revisited, and our CCSD(T) values should be taken as most accurate.

Transthoracic Echocardiography: Beginner's Guide with Emphasis on Blind Spots as Identified with CT and MRI.

Transthoracic echocardiography (TTE) is the primary initial imaging modality in cardiac imaging. Advantages include portability, safety, availability, and ability to assess the morphology and physiology of the heart in a noninvasive manner. Because of this, many patients who undergo advanced imaging with CT or MRI will have undergone prior TTE, particularly when cardiac CT angiography or cardiac MRI is performed. In the modern era, the increasing interconnectivity of picture archiving and communication systems (PACS) has made these images more available for comparison. Therefore, radiologists who interpret chest imaging studies should have a basic understanding of TTE, including its strengths and limitations, to make accurate comparisons and assist in rendering a diagnosis or avoiding a misdiagnosis. The authors present the standard TTE views along with multiplanar reformatted CT images for correlation. This is followed by examples of limitations of TTE, focusing on potential blind spots, which have been placed in seven categories on the basis of the structures involved: (a) pericardium (thickening, calcification, effusions, cysts, masses), (b) aorta (dissection, intramural hematoma, penetrating atherosclerotic ulcer), (c) left ventricular apex (infarcts, aneurysms, thrombus, apical hypertrophic cardiomyopathy), (d) cardiac valves (complications of native and prosthetic valves), (e) left atrial appendage (thrombus), (f) coronary arteries (origins, calcifications, fistulas, aneurysms), and (g) extracardiac structures (primary and metastatic masses). Online supplemental material and the slide presentation from the RSNA Annual Meeting are available for this article . ©RSNA, 2021.

A novel treatment for breast pseudoaneurysm in the anticoagulated patient.

A 74-year-old woman requiring lifetime anticoagulation for antiphospholipid syndrome was noted to develop a pseudoaneurysm (PA) of the breast following core needle biopsy. She was successfully treated via thrombin injection and suffered no complications. In patients requiring anticoagulation, definitive management of PA may be desired. In appropriately selected patients, ultrasound (US)-guided thrombin injection offers superior outcomes to alternative conservative management and obviates the need for surgical intervention.