A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and openshell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr 2 dimer, exploring zeolitecatalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.Keywords quantum chemistry, software, electronic structure theory, density functional theory, electron correlation, computational modelling, Q-Chem Disciplines Chemistry CommentsThis article is from Molecular Physics: An International Journal at the Interface Between Chemistry and Physics 113 (2015): 184, doi:10.1080/00268976.2014. RightsWorks produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted. Authors 185A summary of the technical advances that are incorporated in the fourth major release of the Q-CHEM quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly corre...

Advances in theory and algorithms for electronic structure calculations must be incorporated into program packages to enable them to become routinely used by the broader chemical community. This work reviews advances made over the past five years or so that constitute the major improvements contained in a new release of the Q-Chem quantum chemistry package, together with illustrative timings and applications. Specific developments discussed include fast methods for density functional theory calculations, linear scaling evaluation of energies, NMR chemical shifts and electric properties, fast auxiliary basis function methods for correlated energies and gradients, equation-of-motion coupled cluster methods for ground and excited states, geminal wavefunctions, embedding methods and techniques for exploring potential energy surfaces.

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange–correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear–electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an “open teamware” model and an increasingly modular design.

Summary: Photoinduced electron transfer (PET) is a phenomenon wherein the absorption of light by a chemical species provides an energetic driving force for an electron transfer reaction. 1 – 4 This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics, and photosensitive materials. In recent years, research in the area of photoredox catalysis has leveraged PET for the catalytic generation of both neutral and charged organic free radical species. These technologies have enabled a wide range of previously inaccessible chemical transformations and have seen widespread utilization in both academic and industrial settings. These reactions are often catalyzed by visible-light absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium, or copper. 5 , 6 While a wide variety of closed shell organic molecules have been shown to behave as competent electron transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as an excited state donor or acceptor. This is perhaps somewhat unsurprising in light of previously reported doublet excited state lifetimes for neutral organic radicals, which are typically several orders of magnitude shorter than singlet lifetimes for known transition metal photoredox catalysts. 7 – 11 Herein we document the discovery, characterization, and reactivity of a neutral acridine radical with a maximum excited state oxidation potential of −3.36 V vs. SCE: significantly more reducing than elemental lithium and marking it as one of the most potent chemical reductants reported. 12 Spectroscopic, computational, and chemical studies indicate that the formation of a twisted intramolecular charge transfer species enables the population of higher energy doublet excited states, leading to the observed potent photoreductant behavior. We demonstrate that this catalytically-generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and bodes well for the adoption of this system in additional organic transformations requiring dissolving metal reductants.

Ab initio DFT quantum chemical methods are applied to study intermediates in the catalytic cycle of soluble methane monooxygenase hydroxylase (MMOH), a dinuclear iron-containing enzyme that converts methane and dioxygen selectively to methanol and water. The quantum chemical models reproduce reliably the X-ray crystallographic coordinates of the active site for the oxidized diiron(III) and reduced diiron(II) states to a high degree of structural precision. The results inspired a reexamination of the X-ray structure of reduced MMOH and revealed previously unassigned electron density now attributed to a key structural water molecule. The quantum chemical calculations required construction of a model containing about 100 atoms, which preserved key hydrogen bonding patterns necessary for structural integrity. Smaller models were unstable for the reduced form of the enzyme, an observation with significant mechanistic implications. The large model was then used to investigate the catalytic intermediates Hperoxo, formed upon the addition of dioxygen, and Q, the active species that reacts with methane. The structures, which differ significantly from alternatives proposed in the literature, are consistent with the experimentally available information concerning the spin states, geometries, and thermodynamics of formation of these intermediates. Other models that have been proposed, particularly in the case of Q, are ruled out in our calculations by energetic considerations, which have a simple physical interpretation. A bound water molecule is critical in assembling the catalytically active species Q.