Dispersion corrected r2SCAN based global hybrid functionals: r2SCANh, r2SCAN0, and r2SCAN50

The Journal of Chemical Physics, Journal Year: 2022, Volume and Issue: 156(13)

Published: April 4, 2022

The regularized and restored semilocal meta-generalized gradient approximation (meta-GGA) exchange-correlation functional r2SCAN [Furness et al., J. Phys. Chem. Lett. 11, 8208-8215 (2020)] is used to create three global hybrid functionals with varying admixtures of Hartree-Fock "exact" exchange (HFX). resulting r2SCANh (10% HFX), r2SCAN0 (25% r2SCAN50 (50% HFX) are combined the semi-classical D4 London dispersion correction. new assessed for calculation molecular geometries, main-group, metalorganic thermochemistry at 26 comprehensive benchmark sets. These include extensive GMTKN55 database, ROST61, IONPI19 It shown that a moderate admixture HFX leads relative improvements mean absolute deviations 11% (r2SCANh-D4), 16% (r2SCAN0-D4), 1% (r2SCAN50-D4) compared parental semi-local meta-GGA. For organometallic reaction energies barriers, r2SCAN0-D4 yields an even larger improvement 35%. computation structural parameters (geometry optimization) does not systematically profit from admixture. Overall, best variant performs well both main-group better or on par well-established functionals, such as PW6B95-D4 PBE0-D4. Regarding systems prone self-interaction errors (SIE4x4), shows reasonable performance, reaching quality range-separated ωB97X-V functional. Accordingly, in combination sufficiently converged basis set [def2-QZVP(P)] represents robust reliable choice general use thermochemical properties chemistry.

Language: Английский

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Characterization and heterologous reconstitution of Taxus biosynthetic enzymes leading to baccatin III

Science, Journal Year: 2024, Volume and Issue: 383(6683), P. 622 - 629

Published: Jan. 25, 2024

Paclitaxel is a well known anticancer compound. Its biosynthesis involves the formation of highly functionalized diterpenoid core skeleton (baccatin III) and subsequent assembly phenylisoserinoyl side chain. Despite intensive investigation for half century, complete biosynthetic pathway baccatin III remains unknown. In this work, we identified bifunctional cytochrome P450 enzyme [taxane oxetanase 1 (TOT1)] in

Language: Английский

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Delocalized, asynchronous, closed-loop discovery of organic laser emitters

Science, Journal Year: 2024, Volume and Issue: 384(6697)

Published: May 16, 2024

Contemporary materials discovery requires intricate sequences of synthesis, formulation, and characterization that often span multiple locations with specialized expertise or instrumentation. To accelerate these workflows, we present a cloud-based strategy enabled delocalized asynchronous design-make-test-analyze cycles. We showcased this approach through the exploration molecular gain for organic solid-state lasers as frontier application in optoelectronics. Distributed robotic synthesis in-line property characterization, orchestrated by artificial intelligence experiment planner, resulted 21 new state-of-the-art materials. Gram-scale ultimately allowed verification best-in-class stimulated emission thin-film device. Demonstrating integration five laboratories across globe, workflow provides blueprint delocalizing-and democratizing-scientific discovery.

Language: Английский

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Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Jan. 29, 2024

Abstract We highlight key contributions in the field of direct radical C Ar − H (hetero)aromatic functionalization involving fluorinated radicals. A compilation Functional Group Transfer Reagents and their diverse activation mechanisms leading to release radicals are discussed. The substrate scope for each is analyzed classified into three categories according electronic properties substrates. Density functional theory computational analysis provides insights chemical reactivity several through electrophilicity nucleophilicity parameters. Theoretical reduction potentials also highlights remarkable correlation between oxidizing ability. It established that highly (e.g. ⋅OCF 3 ) capable engaging single‐electron transfer (SET) processes rather than addition, which good agreement with experimental literature data. scale, based on barrier addition these benzene elaborated using high accuracy DLPNO‐(U)CCSD(T) method.

Language: Английский

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Rational design of organic molecules with inverted gaps between the first excited singlet and triplet

Matter, Journal Year: 2024, Volume and Issue: 7(3), P. 1161 - 1186

Published: Jan. 31, 2024

Language: Английский

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