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A formulation of analytic energy first derivatives for the coupled-cluster singles and doubles augmented with noniterative triples [CCSD(T)] method with spin-orbit coupling included at the orbital level and an implementation for evaluation of first-order properties are reported. The standard density-matrix formulation for analytic CC gradient theory adapted to complex algebra has been used. The orbital-relaxation contributions from frozen core, occupied, virtual, and frozen virtual orbitals to analytic spin-orbit CCSD(T) gradients are fully taken into account and treated efficiently, which is of importance to calculations of heavy elements. Benchmark calculations of first-order properties including dipole moments and electric-field gradients using the corresponding exact two-component property integrals are presented for heavy-element containing molecules to demonstrate the applicability and usefulness of the present analytic scheme.A new spin-averaged potential energy surface (PES) for non-reactive O2(Σg-3) + O2(Σg-3) collisions is presented. The potential is formulated analytically according to the nature of the principal interaction components, with the main van der Waals contribution described through the improved Lennard-Jones model. All the parameters involved in the formulation, having a physical meaning, have been modulated in restricted variation ranges, exploiting a combined analysis of experimental and ab initio reference data. The new PES is shown to be able to reproduce a wealth of different physical properties, ranging from the second virial coefficients to transport properties (shear viscosity and thermal conductivity) and rate coefficients for inelastic scattering collisions. Rate coefficients for the vibrational inelastic processes of O2, including both vibration-to-vibration (V-V) and vibration-to-translation/rotation (V-T/R) energy exchanges, were then calculated on this PES using a mixed quantum-classical method. The effective formulation of the potential and its combination with an efficient, yet accurate, nuclear dynamics treatment allowed for the determination of a large database of V-V and V-T/R energy transfer rate coefficients in a wide temperature range.The recently proposed r2SCAN meta-generalized-gradient approximation (mGGA) of Furness and co-workers is used to construct an efficient composite electronic-structure method termed r2SCAN-3c. To this end, the unaltered r2SCAN functional is combined with a tailor-made triple-ζ Gaussian atomic orbital basis set as well as with refitted D4 and geometrical counter-poise corrections for London-dispersion and basis set superposition error. The performance of the new method is evaluated for the GMTKN55 database covering large parts of chemical space with about 1500 data points, as well as additional benchmarks for non-covalent interactions, organometallic reactions, and lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. AZD0156 research buy These comprehensive tests reveal a spectacular performance and robustness of r2SCAN-3c It by far surpasses its predecessor B97-3c at only twice the cost and provides one of the best results of all semi-local density-functional theory (DFT)/QZ methods ever tested for the GMTKN55 database at one-tenth of the cost. Specifically, for reaction and conformational energies as well as non-covalent interactions, it outperforms prominent hybrid-DFT/QZ approaches at two to three orders of magnitude lower cost. Perhaps, the most relevant remaining issue of r2SCAN-3c is self-interaction error (SIE), owing to its mGGA nature. However, SIE is slightly reduced compared to other (m)GGAs, as is demonstrated in two examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous composite DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.We present a two-level iterative solver for linear response time-dependent density functional theory by combining two forms of the Casida equation in the Kohn-Sham orbital representation and in Hutter's formulation. This two-level iterative solver has been implemented with the plane wave pseudopotential method for excited-state simulations of molecular and low-dimensional solid materials. Numerical studies with the Davidson algorithm demonstrate that this two-level iterative solver yields excited-state properties for molecules (benzene C6H6 and fullerene C60) and low-dimensional semiconductors [two-dimensional molybdenum disulfide MoS2 monolayer and rutile titanium dioxide TiO2(110) surface] with significantly reduced computational cost and storage requirement compared with standard iterative algorithms. We apply our approach to investigate the photoinduced charge separation of methanol molecules adsorption on the rutile TiO2(110) surface from the exciton perspective and validate that the photogenerated hole can be captured by methanol molecules.Nonadiabatic phenomena are investigated in the rovibrational motion of molecules confined in an infrared cavity. Conical intersections (CIs) between vibrational polaritons, similar to CIs between electronic polaritonic surfaces, are found. The spectral, topological, and dynamic properties of the vibrational polaritons show clear fingerprints of nonadiabatic couplings between molecular vibration, rotation, and the cavity photonic mode. Furthermore, it is found that for the investigated system, composed of two rovibrating HCl molecules and the cavity mode, breaking the molecular permutational symmetry, by changing   35Cl to   37Cl in one of the HCl molecules, the polaritonic surfaces, nonadiabatic couplings, and related spectral, topological, and dynamic properties can deviate substantially. This implies that the natural occurrence of different molecular isotopologues needs to be considered when modeling realistic polaritonic systems.We combine a regularized variant of the strongly constrained and appropriately normed semilocal density functional [J. Sun, A. Ruzsinszky, and J. P. Perdew, Phys. Rev. Lett. 115, 036402 (2015)] with the latest generation semi-classical London dispersion correction. The resulting density functional approximation r2SCAN-D4 has the speed of generalized gradient approximations while approaching the accuracy of hybrid functionals for general chemical applications. We demonstrate its numerical robustness in real-life settings and benchmark molecular geometries, general main group and organo-metallic thermochemistry, and non-covalent interactions in supramolecular complexes and molecular crystals. Main group and transition metal bond lengths have errors of just 0.8%, which is competitive with hybrid functionals for main group molecules and outperforms them for transition metal complexes. The weighted mean absolute deviation (WTMAD2) on the large GMTKN55 database of chemical properties is exceptionally small at 7.5 kcal/mol.AZD0156 research buy