[This corrects the article DOI: 10.1098/rsos.171563.].
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7062091 | PMC |
http://dx.doi.org/10.1098/rsos.200115 | DOI Listing |
ACS Omega
January 2025
Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia.
O-Protected oxacarbenium ions are key intermediates of glycosylation reactions. The knowledge of their conformational preferences is crucial for choosing the correct blocking group pattern to achieve the required stereochemical outcome. This article describes a computational study of several glucosyl oxacarbenium cations.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Institute of Materials, China Academy of Engineering Physics, Mianyang, Sichuan 621907, China.
Hubbard-corrected density-functional theory (DFT+) is widely employed to predict the physical properties of correlated materials; however, reliable predictions can be hindered by the presence of metastable solutions in the DFT+ calculations. This issue stems from the orbital physics inherent in DFT+. To address this, we propose a method to circumvent metastable states by applying a random orbital-dependent local perturbation to the localized orbitals.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Energy decomposition analysis (EDA) based on density functional theory (DFT) and self-consistent field (SCF) calculations has become widely used for understanding intermolecular interactions. This work reports a new approach to EDA for post-SCF wave functions based on closed-shell restricted second-order Mo̷ller-Plesset (MP2) together with an efficient implementation that generalizes the successful SCF-level second-generation absolutely localized molecular orbital EDA approach, ALMO-EDA-II, and improves upon MP2 ALMO-EDA-I. The new MP2 ALMO-EDA-II provides distinct energy contributions for a frozen interaction energy containing permanent electrostatics and Pauli repulsions, polarized energy-yielding induced electrostatics, dispersion-corrected energy, and the fully relaxed energy, which describes charge transfer.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Department of Chemistry, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, Korea.
Practical density-corrected density functional theory (DC-DFT) calculations rely on Hartree-Fock (HF) densities, which can be computationally expensive for systems with over a hundred atoms. We extend the applicability of HF-DFT using the dual-basis method, where the density matrix from a smaller basis set is used to estimate the HF solution on a larger basis set. Benchmarks on many systems, including the GMTKN55 database for main-group chemistry, and the L7 and S6L data sets for large molecular systems demonstrate the efficacy of our approach.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Pharmacy, Yantai University, Yantai 264005, P. R. China.
Compared with the energetically favorable 5- or 6-membered fluoro-functionalized heterocycles, the construction of medium-sized fluoro-heterocycles is relatively under-researched because of their inherently unfavorable enthalpic and entropic nature. Based on rational design and DFT calculations, a novel photocatalytic difluoromethyl radical-initiated intramolecular 7--trig cyclization was realized, thus affording a sustainable route for the synthesis of challenging fluoro-functionalized medium-sized -heterocycles. Depending on atomic dipole moment corrected Hirshfeld population (ADCH) charge calculations, the chemoselective 6--trig radical cyclizations were further replenished.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!