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.

QM/MM calculations of electronic excitations with diffuse basis sets often have large errors due to spill-out of electrons from the quantum subsystem. The Pauli repulsion of the electrons by the environment has to be included to avoid this. We propose transferable atomic all-electron pseudopotentials that can readily be combined with most MM force fields to avoid electron spill-out. QM/MM excitation energies computed with time-dependent Hartree–Fock and the algebraic diagrammatic construction through second-order are benchmarked against supermolecular calculations to validate these new pseudopotentials. The QM/MM calculations with pseudopotentials give accurate results that are stable with augmentation of the basis set with diffuse functions. We show that the largest contribution to residual deviations from full QM calculations is caused by the missing London dispersion interaction.

We consider different Linear Combination of Unitaries (LCU) decompositions for molecular electronic structure Hamiltonians. Using these LCU decompositions for Hamiltonian simulation on a quantum computer, the main figure of merit is the 1-norm of their coefficients, which is associated with the quantum circuit complexity. It is derived that the lowest possible LCU 1-norm for a given Hamiltonian is half of its spectral range. This lowest norm decomposition is practically unattainable for general Hamiltonians; therefore, multiple practical techniques to generate LCU decompositions are proposed and assessed. A technique using symmetries to reduce the 1-norm further is also introduced. In addition to considering LCU in the Schrödinger picture, we extend it to the interaction picture, which substantially further reduces the 1-norm.

We present an implementation of analytic gradients for electronically excited states for the algebraic-diagrammatic construction through second order, ADC(2), in combination with the conductor-like screening model (COSMO) as an implicit solvent model. The implementation uses a post-SCF reaction field scheme for the coupling between the environment and the quantum system which retains the computational efficiency of the gas-phase RI-ADC(2) calculations. Applying this approach, we computed solvatochromic shifts for UV absorption and fluorescence transitions of 4-(N,N-dimethylamino)benzonitrile using equilibrium geometries for the ground and the first excited states optimized in the presence of acetonitrile as solvent. Furthermore, we investigated the excited state energies and geometries of the 2-iodobenzimidazolium·triflate ion pair in aqueous solution as an example where solvent effects have a large influence on the structure and the UV spectrum.

Many synthetic DNA minor groove binders exhibit a strong increase in fluorescence when bound to DNA. The pharmaceutical-relevant berenil (diminazene aceturate) is an exception with an extremely low fluorescence quantum yield (on the order of 10). We investigate the ultrafast excited-state dynamics of this triazene by femtosecond time-resolved fluorescence experiments in water, ethylene glycol, and buffer and bound to the enzyme β-trypsin, the minor groove of AT-rich DNA, and G-quadruplex DNA. Ab initio calculations provide additional mechanistic insight. The complementing studies unveil that the excited-state motion initiated by ππ* excitation occurs in two phases: a subpicosecond phase associated with the lengthening of the central N═N double bond, followed by a bicycle-pedal-type motion of the triazene bridge, which is almost volume-conserving and can proceed efficiently within only a few picoseconds even under spatially confined conditions. Our results elucidate the excited-state relaxation mechanism of aromatic triazenes and explain the modest sensitivity of the fluorescence quantum yield of berenil even when it is bound to various biomolecules.