We propose to construct electron correlation methods that are scalable in both molecule size and aggregated parallel computational power, in the sense that the total elapsed time of a calculation becomes nearly independent of the molecular size when the number of processors grows linearly with the molecular size. This is shown to be possible by exploiting a combination of local approximations and parallel algorithms. The concept is demonstrated with a linear scaling pair natural orbital local second-order Møller-Plesset perturbation theory (PNO-LMP2) method. In this method, both the wave function manifold and the integrals are transformed incrementally from projected atomic orbitals (PAOs) first to orbital-specific virtuals (OSVs) and finally to pair natural orbitals (PNOs), which allow for minimum domain sizes and fine-grained accuracy control using very few parameters. A parallel algorithm design is discussed, which is efficient for both small and large molecules, and numbers of processors, although true inverse-linear scaling with compute power is not yet reached in all cases. Initial applications to reactions involving large molecules reveal surprisingly large effects of dispersion energy contributions as well as large intramolecular basis set superposition errors in canonical MP2 calculations. In order to account for the dispersion effects, the usual selection of PNOs on the basis of natural occupation numbers turns out to be insufficient, and a new energy-based criterion is proposed. If explicitly correlated (F12) terms are included, fast convergence to the MP2 complete basis set (CBS) limit is achieved. For the studied reactions, the PNO-LMP2-F12 results deviate from the canonical MP2/CBS and MP2-F12 values by <1 kJ mol(-1), using triple-ζ (VTZ-F12) basis sets.

A well-parallelized local singles and doubles coupled-cluster (LCCSD) method using pair natural virtual orbitals (PNOs) is presented. The PNOs are constructed using large domains of projected atomic orbitals (PAOs) and orbital specific virtual orbitals (OSVs). We introduce a hierarchy of close, weak, and distant pairs, based on pair energies evaluated by local Møller-Plesset perturbation theory (LMP2). In contrast to most previous implementations of LCCSD methods, the close and weak pairs are not approximated by LMP2 but treated by higher-order methods. This leads to greatly improved accuracy for large systems, in particular when long-range dispersion interactions are important. Close pair amplitudes are optimized using approximate LCCSD equations, in which slowly decaying terms that mutually cancel at long-range are neglected. For weak pairs, the same approximations are used, but in addition, the nonlinear terms are neglected (coupled electron pair approximation). Distant pairs are treated by spin-component scaled (SCS)-LMP2 using multipole approximations. For efficiency reasons, various projection approximations are also introduced. The impact of these approximations on absolute and relative energies depends on the PNO domain sizes. The errors are found to be negligible, provided that sufficiently large PNO domains are used for close and weak pairs. For the selection of these domains the usual natural orbital occupation number criterion is found to be insufficient, and an additional energy criterion is used. For extended one-dimensional systems, the computational effort of the method scales nearly linearly with the number of correlated electrons, but the linear scaling regime is usually not reached in real-life applications for three-dimensional systems. Nevertheless, due to the parallelization that is efficient up to about 100-200 CPU cores (dependent on the molecular size), accurate calculations for three-dimensional molecules with about 100 atoms and augmented triple-ζ basis sets (e.g., cc-pVTZ-F12) can be carried out in 1-3 h of elapsed time (depending on the molecular structure and the number of CPU cores, excluding the time for Hartree-Fock). The convergence of the results with respect to the thresholds and options that control the domain, pair, and projection approximations is extensively tested. Benchmark examples for several difficult and large cases are presented, which demonstrate that the errors of relative energies (e.g., reaction energies, barrier heights) caused by the pair and projection approximations can be reduced to below 1 kJ mol. The remaining errors are mainly caused by the finite PAO domains. The larger these are made, the more intramolecular or intermolecular basis set superposition errors are introduced, and the canonical results are approached only very slowly. This problem is eliminated in the explicitly correlated variant of our method (PNO-LCCSD-F12), which will be described in a separate paper, along with a larger set of benchmark calculations.

We present an efficient explicitly correlated pair natural orbital local coupled cluster (PNO-LCCSD-F12) method. The method is an extension of our previously reported PNO-LCCSD approach ( Schwilk et al., J. Chem. Theory Comput. 2017 , 13 , 3650 - 3675 ). Near linear scaling with the molecular size is achieved by using pair, domain, and projection approximations, local density fitting and local resolution of the identity, and by exploiting the sparsity of the local molecular orbitals as well as of the projected atomic orbitals. The effect of the various domain approximations is tested for a wide range of chemical reactions and intermolecular interactions. In accordance with previous findings, it is demonstrated that the F12 terms significantly reduce the domain errors. The convergence of the reaction and interaction energies with respect to the parameters that determine the domain sizes and pair approximations is extensively tested. The results obtained with our default thresholds agree within a few tenths of a kcal mol with the ones computed with very tight options. For cases where canonical calculations are still feasible, the relative energies of local and canonical calculations agree within similar error bounds. The PNO-LCCSD-F12 method needs only 25-40% more computer time than a corresponding PNO-LCCSD calculation while greatly improving the accuracy. Our program is well parallelized and capable of computing accurate correlation energies for molecules with more than 150 atoms using augmented triple-ζ basis sets and more than 5000 basis functions. Using several nodes of a small computer cluster, such calculations can be carried out within a few hours.

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Cross sections, rates, equilibrium constants and vibrational relaxation times for the N(4S) + O2(X3Σ−g) ↔ O(3P) + NO(X2Π) reaction from simulations on new, RKHS-based surfaces for the three lowest electronic states.

Computational quantum mechanics based molecular and materials design campaigns consume increasingly more high-performance compute resources, making improved job scheduling efficiency desirable in order to reduce carbon footprint or wasteful spending. We introduce quantum machine learning (QML) models of the computational cost of common quantum chemistry tasks. For single point, geometry optimization, and transition state calculations the out of sample prediction error of QML models of wall times decays systematically with training set size. We present numerical evidence for thousands of organic molecular systems including closed and open shell equilibrium structures, as well as transition states. Levels of electronic structure theory considered include B3LYP/def2-TZVP, MP2/6-311G(d), local CCSD(T)/VTZ-F12, CASSCF/VDZ-F12, and MRCISD+Q-F12/VDZ-F12. In comparison to conventional indiscriminate job treatment, QML based wall time predictions significantly improve job scheduling efficiency for all tasks after training on just thousands of molecules. Resulting reductions in CPU time overhead range from 10% to 90%.

The compounds [Fe(CO) (dRpf)] , n=0, 1, 2 and dRpf=1,1'-bis(dicyclohexylphosphino)ferrocene ([1] ) or 1,1'-bis(diisopropylphosphino)ferrocene ([2] ), were obtained as two-step reversible redox systems by photolytic and redox reactions. The iron-iron distance decreases from about 4 Å to about 3 Å on oxidation, which takes place primarily at the tricarbonyliron moiety. Whereas ferrocene oxidation is calculated to occur only in excited states, the near infrared absorptions of the mixed-valent monocations are due to an unprecedented "inverse" inter-valence charge transfer from the electron-rich iron(II) in the ferrocene backbone to the electron-deficient tricarbonyliron(I). Protonation of complex 1 results in the formation of the structurally characterized hydride [1H]BF , which reacts with acetone to form the dication, 1 , and isopropanol. While the hydride [2H]BF was found to be unstable, protonation of 2 in acetone resulted in the clean formation of 2 formally a hydrogen transfer.

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