The existence of divalent bis(pentaisopropylcyclopentadienyl) actinocene compounds, An(Cp^iPr₅)₂ (An = Th, U, Pu, Am, Bk, No, and Lr), is assessed by density functional theory (DFT) calculations with scalar-relativistic small-core pseudopotentials. The calculations predict ground states with significant 6d occupation for Th, U, and Lr, whereas Am, Bk, and No exhibit 5f ground states. A mixed ground state with predominant 5f character is found for Pu. The complexes exhibit a linear coordination geometry and high S₁₀ symmetry except for Pu(Cp^iPr₅)₂ and Am(Cp^iPr₅)₂, which are found to be bent by 11 and 12°, respectively. Absorption spectra are simulated with time-dependent density functional theory (TD-DFT) and compared to experimental spectra of known tris(C₄H₄SiMe₃) and tris(C₅H₃(SiMe₃)₂) compounds [ J. Am. Chem. Soc. 2015 , 137 , 369 - 382 . DOI: 10.1021/ja510831n ] as well as recently synthesized divalent lanthanide analogs Dy(Cp^iPr₅)₂ and Tb(Cp^iPr₅)₂ [ J. Am. Chem. Soc. , 2019 , 141 , 12967 - 12973 . DOI: 10.1021/jacs.9b05816 ]. Thermodynamic stability is assessed by calculation of adiabatic reduction potentials of the trivalent precursors [An(Cp^iPr₅)₂]⁺, and the feasibility of further reduction to obtain as yet unknown monovalent molecular actinide complexes is discussed.

The natural determinant reference (NDR) or principal natural determinant is the Slater determinant comprised of the N most strongly occupied natural orbitals of an N-electron state of interest. Unlike the Kohn–Sham (KS) determinant, which yields the exact ground-state density, the NDR only yields the best idempotent approximation to the interacting one-particle reduced density matrix, but it is well-defined in common atom-centered basis sets and is representation-invariant. We show that the under-determination problem of prior attempts to define a ground-state energy functional of the NDR is overcome in a grand-canonical ensemble framework at the zero-temperature limit. The resulting grand potential functional of the NDR ensemble affords the variational determination of the ground state energy, its NDR (ensemble), and select ionization potentials and electron affinities. The NDR functional theory can be viewed as an “exactification” of orbital optimization and empirical generalized KS methods. NDR functionals depending on the noninteracting Hamiltonian do not require troublesome KS-inversion or optimized effective potentials.

We report a set of brominated luciferins for bioluminescence imaging. These regioisomeric scaffolds were accessed by using a common synthetic route. All analogues produced light with firefly luciferase, although varying levels of emission were observed. Differences in photon output were analyzed by computation and photophysical measurements. The brightest brominated luciferin was further evaluated in cell and animal models. At low doses, the analogue outperformed the native substrate in cells. The remaining luciferins, although weak emitters with firefly luciferase, were inherently capable of light production and thus potential substrates for orthogonal mutant enzymes.

TURBOMOLE is a collaborative, multi-national software development project aiming to provide highly efficient and stable computational tools for quantum chemical simulations of molecules, clusters, periodic systems, and solutions. The TURBOMOLE software suite is optimized for widely available, inexpensive, and resource-efficient hardware such as multi-core workstations and small computer clusters. TURBOMOLE specializes in electronic structure methods with outstanding accuracy-cost ratio, such as density functional theory including local hybrids and the random phase approximation (RPA), GW-Bethe-Salpeter methods, second-order Møller-Plesset theory, and explicitly correlated coupled-cluster methods. TURBOMOLE is based on Gaussian basis sets and has been pivotal for the development of many fast and low-scaling algorithms in the past three decades, such as integral-direct methods, fast multipole methods, the resolution-of-the-identity approximation, imaginary frequency integration, Laplace transform, and pair natural orbital methods. This review focuses on recent additions to TURBOMOLE's functionality, including excited-state methods, RPA and Green's function methods, relativistic approaches, high-order molecular properties, solvation effects, and periodic systems. A variety of illustrative applications along with accuracy and timing data are discussed. Moreover, available interfaces to users as well as other software are summarized. TURBOMOLE's current licensing, distribution, and support model are discussed, and an overview of TURBOMOLE's development workflow is provided. Challenges such as communication and outreach, software infrastructure, and funding are highlighted.