Ten simple gas-phase, main-group as well as transition-metal, mixed-valence (MV) oxo complexes are suggested for the screening of electronic-structure methods for the computational study of localization vs delocalization of charge and spin density in MV systems, without the usual added complication of environmental effects. Benchmark coupled-cluster energies up to CCSDT(Q)/CBS (for AlO, SiO, SiO, ScO, TiO) and CCSD(T)/CBS (for TiO, TiO, VO, CrO) quality are provided as a basis for screening a variety of density-functional methods, ranging from a generalized gradient approximation via global and range-separated to local hybrid functionals. Additionally, experimental evidence for a delocalized D structure of the somewhat larger VO is used. None of the functionals is fully satisfactory when tasked with describing simultaneously the most extreme cases, the localized AlO and the delocalized VO. While relatively large exact-exchange admixtures are required for the former, and for related localized cases, lower ones are preferable for the latter, as well for other delocalized dd systems. The overall best combined performance is provided by a Lh-SVWN (g(r) = 0.670 τ/τ) local hybrid, the MN15 global hybrid, and the ωB97X-D range-separated hybrid. We also provide vibrational data for comparison with experiment.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.jctc.8b00289 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Basic Science and Pathogenesis.
Alzheimers Dement
December 2024
Columbia University Irving Medical Center, New York, NY, USA.
Background: Glial cells exhibit distinct transcriptional responses to β-amyloid pathology in Alzheimer's disease (AD). While sophisticated single-cell based methods have revealed heterogeneous glial subpopulations in the human AD brain, the histological localization of these multicellular responses to AD pathology has not been fully characterized due to the loss of spatial information. Here, we combined spatial transcriptomics (ST) with immunohistochemistry to explore the molecular mechanisms in the neuritic plaque niche.
View Article and Find Full Text PDFA Case of Leukemia Cutis (Acute Myeloid Leukemia) With Epidermotropism.
Am J Dermatopathol
December 2024
Department of Dermatology, Columbia University, New York, NY.
Acute myeloid leukemia is a cancer involving uncontrolled proliferation of hematopoietic cells. Cutaneous involvement is referred to as leukemia cutis (LC). The histopathologic presentation of LC is variable, and may present with perivascular, periadnexal, dermal, or subcutaneous infiltrate.
View Article and Find Full Text PDFEnabling simultaneous photoluminescence spectroscopy and X-ray footprinting mass spectrometry to study protein conformation and interactions.
Anal Methods
January 2025
Molecular Foundry Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
X-ray footprinting mass spectrometry (XFMS) is a structural biology method that uses broadband X-rays for hydroxyl radical labeling to map protein interactions and conformation in solution. However, while XFMS alone provides important structural information on biomolecules, as we move into the era of the interactome, hybrid methods are becoming increasingly necessary to gain a comprehensive understanding of protein complexes and interactions. Toward this end, we report the development of the first synergetic application of inline and real-time fluorescent spectroscopy at the Advanced Light Source's XFMS facility to study local protein interactions and global conformational changes simultaneously.
View Article and Find Full Text PDFLipophilicity Modulation of Fluorescent Probes for Imaging of Cellular Microvesicle Dynamics.
J Am Chem Soc
January 2025
School of Chemistry and Chemical Engineering, Institute of Physical Science and Information Technology, Information Materials and Intelligent Sensing Laboratory of Anhui Province, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University, Hefei, Anhui 230601, China.
Real-time monitoring of dynamic microvesicles (MVs), vesicles associated with living cells, is of great significance in deeply understanding their origin, transport, and function. However, specific labeling MVs poses a challenge due to the lack of unique biomarkers that differentiate them from other cellular compartments. Here, we present a strategy to selectively label MVs by evaluating a series of lipid layer-sensitive cationic indolium-coumarin fluorescent probes (designated as IC-C, with ranging from 1 to 18) that feature varying aliphatic side chains (CH).
View Article and Find Full Text PDFApplication of an improved ant colony optimization algorithm of hybrid strategies using scheduling for patient management in hospitals.
Heliyon
November 2024
Department of Industrial & Production Engineering, Rajshahi University of Engineering & Technology (RUET), Rajshahi- 6204, Bangladesh.
To balance the convergence speed and solution diversity and enhance optimization performance when addressing large-scale optimization problems, this research study presents an improved ant colony optimization (ICMPACO) technique. Its foundations include the co-evolution mechanism, the multi-population strategy, the pheromone diffusion mechanism, and the pheromone updating method. The suggested ICMPACO approach separates the ant population into elite and common categories and breaks the optimization problem into several sub-problems to boost the convergence rate and prevent slipping into the local optimum value.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!