The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations

Hyperion: A New Computational Tool for Relativistic Ab Initio Hyperfine Coupling

[Image: see text] Herein we describe Hyperion, a new program for computing relativistic picture-change-corrected magnetic resonance parameters from scalar relativistic active space wave functions, with or without spin–orbit coupling (SOC) included a posteriori. Hyperion also includes a new orbital decomposition method for assisting active space selection for calculations of hyperfine coupling. For benchmarking purposes, we determine hyperfine coupling constants of selected alkali metal, transition metal, and lanthanide atoms, based on complete active space self-consistent field spin–orbit calculations in OpenMolcas. Our results are in excellent agreement with experimental data from atomic spectroscopy as well as theoretical predictions from four-component relativistic calculations

Relaxation and ligand hyperfine effects in an isostructural early lanthanide series [Ln(Cptt)3] (Ln = Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) by pulsed EPR spectroscopy

We examine lanthanide (Ln)-ligand bonding in a family of early Ln3+ complexes [Ln(Cptt)3] (1-Ln, Ln = La, Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin T1 and Tm relaxation times of 12 and 0.2 μs (1-Nd), 89 and 1 μs (1-Ce) and 150 and 1.7 μs (1-Sm), respectively, at 5 K: the T1 relaxation of 1-Nd is more than 102 times faster than its valence isolelectronic uranium analogue. 13C and 1H hyperfine sublevel correlation (HYSCORE) spectroscopy reveals that the extent of covalency is negligible in these Ln compounds, with much smaller hyperfine interactions than observed for equivalent actinide (Th and U) complexes. This is corroborated by ab initio calculations, confirming the predominant electrostatic nature of the metal-ligand bonding in these complexes

A Continuous Multistep Process for the Preparation of 3-Bromo-2-Oxopropanal O-methyl Oxime as a Precursor to Access C4-Oxime-Substituted Thiazoles

We report a strategy designed for the rapid and convergent assembly of C4-oxime substituted thiazoles. Our approach relied on 3-bromo-2-oxopropanal O-methyl oxime as a key building block. In particular, we describe a multistep continuous synthesis of this intermediate and demonstrate the advantages of our set-up upon scaling up

Metal-carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy

We examine lanthanide (Ln)-ligand bonding in a family of early Ln3+ complexes [Ln(Cptt)3] (1-Ln, Ln = La, Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin T1 and Tm relaxation times of 12 and 0.2 μs (1-Nd), 89 and 1 μs (1-Ce) and 150 and 1.7 μs (1- Sm), respectively, at 5 K: the T1 relaxation of 1-Nd is more than 102 times faster than its valence isolelectronic uranium analogue.  13C and 1H hyperfine sublevel correlation (HYSCORE) spectroscopy reveals that the extent of covalency is negligible in these Ln compounds, with much smaller hyperfine interactions than observed for equivalent actinide (Th and U) complexes. This is corroborated by ab initio calculations, confirming the predominant electrostatic nature of the metal-ligand bonding in these complexes.<br/

A Convergent Continuous Multistep Process for the Preparation of C₄‑Oxime-Substituted Thiazoles

We report a strategy designed for the rapid and convergent assembly of C₄-oxime substituted thiazoles. Our approach relied on 3-bromo-2-oxopropanal <i>O</i>-methyl oxime <b>7</b> as a key building block. A three-step sequence to <b>7</b> was designed, which, for safety concerns, could only be operated in batch mode on limited scales (≪100 g). We describe herein how we addressed such a limitation, by designing a multistep continuous synthesis of this intermediate and further demonstrate the advantages of flow reactor configuration upon scaling up

The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.ISSN:1549-9618ISSN:1549-962

The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.</p

The OpenMolcas <i>Web</i>: A Community-Driven Approach to Advancing Computational Chemistry

The developments of the open-source Open-Molcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations