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We present the ioChem-BD platform ( www.iochem-bd.org ) as a multiheaded tool aimed to manage large volumes of quantum chemistry results from a diverse group of already common simulation packages. The platform has an extensible structure. The key modules managing the main tasks are to (i) upload of output files from common computational chemistry packages, (ii) extract meaningful data from the results, and (iii) generate output summaries in user-friendly formats. A heavy use of the Chemical Mark-up Language (CML) is made in the intermediate files used by ioChem-BD. From them and using XSL techniques, we manipulate and transform such chemical data sets to fulfill researchers' needs in the form of HTML5 reports, supporting information, and other research media.

The mechanism of the light‐induced spin crossover of the [Fe(bpy)3]2+ complex (bpy=2,2′‐bipyridine) has been studied by combining accurate electronic‐structure calculations and time‐dependent approaches to calculate intersystem‐crossing rates. We investigate how the initially excited metal‐to‐ligand charge transfer (MLCT) singlet state deactivates to the final metastable high‐spin state. Although ultrafast X‐ray free‐electron spectroscopy has established that the total timescale of this process is on the order of a few tenths of a picosecond, the details of the mechanisms still remain unclear. We determine all the intermediate electronic states along the pathway from low spin to high spin and give estimates for the deactivation times of the different stages. The calculations result in a total deactivation time on the same order of magnitude as the experimentally determined rate and indicate that the complex can reach the final high‐spin state by means of different deactivation channels. The optically populated excited singlet state rapidly decays to a triplet state with an Fe d6() configuration either directly or by means of a triplet MLCT state. This triplet ligand‐field state could in principle decay directly to the final quintet state, but a much faster channel is provided by internal conversion to a lower‐lying triplet state and subsequent intersystem crossing to the high‐spin state. The deactivation rate to the low‐spin ground state is much smaller, which is in line with the large quantum yield reported for the process.

The nature and magnitude of the magnetic anisotropy of heptacoordinate mononuclear Ni(II) and Co(II) complexes were investigated by a combination of experiment and ab initio calculations. The zero-field splitting (ZFS) parameters D of [Ni(H(2)DAPBH)(H(2)O)(2)](NO(3))(2)⋅2 H(2)O (1) and [Co(H(2)DAPBH)(H(2)O)(NO(3))](NO(3)) [2; H(2)DAPBH = 2,6-diacetylpyridine bis- (benzoyl hydrazone)] were determined by means of magnetization measurements and high-field high-frequency EPR spectroscopy. The negative D value, and hence an easy axis of magnetization, found for the Ni(II) complex indicates stabilization of the highest M(S) value of the S = 1 ground spin state, while a large and positive D value, and hence an easy plane of magnetization, found for Co(II) indicates stabilization of the M(S) = ±1/2 sublevels of the S = 3/2 spin state. Ab initio calculations were performed to rationalize the magnitude and the sign of D, by elucidating the chemical parameters that govern the magnitude of the anisotropy in these complexes. The negative D value for the Ni(II) complex is due largely to a first excited triplet state that is close in energy to the ground state. This relatively small energy gap between the ground and the first excited state is the result of a small energy difference between the d(xy) and d(x(2)-y(2)) orbitals owing to the pseudo-pentagonal-bipyramidal symmetry of the complex. For Co(II), all of the excited states contribute to a positive D value, which accounts for the large magnitude of the anisotropy for this complex.

Progress in nanotechnology requires new approaches to materials synthesis that make it possible to control material functionality down to the smallest scales. An objective of materials research is to achieve enhanced control over the physical properties of materials such as ferromagnets, ferroelectrics and superconductors. In this context, complex oxides and inorganic perovskites are attractive because slight adjustments of their atomic structures can produce large physical responses and result in multiple functionalities. In addition, these materials often contain ferroelastic domains. The intrinsic symmetry breaking that takes place at the domain walls can induce properties absent from the domains themselves, such as magnetic or ferroelectric order and other functionalities, as well as coupling between them. Moreover, large domain wall densities create intense strain gradients, which can also affect the material's properties. Here we show that, owing to large local stresses, domain walls can promote the formation of unusual phases. In this sense, the domain walls can function as nanoscale chemical reactors. We synthesize a two-dimensional ferromagnetic phase at the domain walls of the orthorhombic perovskite terbium manganite (TbMnO3), which was grown in thin layers under epitaxial strain on strontium titanate (SrTiO3) substrates. This phase is yet to be created by standard chemical routes. The density of the two-dimensional sheets can be tuned by changing the film thickness or the substrate lattice parameter (that is, the epitaxial strain), and the distance between sheets can be made as small as 5 nanometres in ultrathin films, such that the new phase at domain walls represents up to 25 per cent of the film volume. The general concept of using domain walls of epitaxial oxides to promote the formation of unusual phases may be applicable to other materials systems, thus giving access to new classes of nanoscale materials for applications in nanoelectronics and spintronics.

No abstract

The performance of the complete active space second-order perturbation theory (CASPT2) to accurately predict magnetic coupling in a wide series of molecules and solid state compounds has been established. It is shown that CASPT2, based on a reference wave function that only includes the effects described by the Anderson or Hay−Thibeault−Hoffmann model, correctly reproduces all experimental trends. For a complete quantitative agreement with experiment (or with accurate results arising from the difference dedicated configuration interaction method), it is necessary to include effects that go beyond the Anderson model in the reference wave function. The CASPT2 method is computationally less demanding than CI based methods and, hence, allows us to extend the study of magnetic coupling parameters to larger molecules or systems with elevated spin moments. Moreover, CASPT2 provides a reliable and accurate alternative to density functional based methods that require the use of a broken symmetry approach.

The electronic structure relevant to low spin (LS)↔high spin (HS) transitions in Fe(II) coordination compounds with a FeN6 core are studied. The selected [Fe(tz)6]2+ (1) (tz = 1H-tetrazole), [Fe(bipy)3]2+ (2) (bipy = 2,2′-bipyridine), and [Fe(terpy)2]2+ (3) (terpy = 2,2′:6′,2″-terpyridine) complexes have been actively studied experimentally, and with their respective mono-, bi-, and tridentate ligands, they constitute a comprehensive set for theoretical case studies. The methods in this work include density functional theory (DFT), time-dependent DFT (TD-DFT), and multiconfigurational second order perturbation theory (CASPT2). We determine the structural parameters as well as the energy splitting of the LS–HS states (ΔEHL) applying the above methods and comparing their performance. We also determine the potential energy curves representing the ground and low-energy excited singlet, triplet, and quintet d6 states along the mode(s) that connect the LS and HS states. The results indicate that while DFT is well suited for the prediction of structural parameters, an accurate multiconfigurational approach is essential for the quantitative determination of ΔEHL. In addition, a good qualitative agreement is found between the TD-DFT and CASPT2 potential energy curves. Although the TD-DFT results might differ in some respect (in our case, we found a discrepancy at the triplet states), our results suggest that this approach, with due care, is very promising as an alternative for the very expensive CASPT2 method. Finally, the two-dimensional (2D) potential energy surfaces above the plane spanned by the two relevant configuration coordinates in [Fe(terpy)2]2+ were computed at both the DFT and CASPT2 levels. These 2D surfaces indicate that the singlet–triplet and triplet–quintet states are separated along different coordinates, i.e., different vibration modes. Our results confirm that in contrast to the case of complexes with mono- and bidentate ligands, the singlet–quintet transitions in [Fe(terpy)2]2+ cannot be described using a single configuration coordinate.