| 1. |
- Delcey, Mickael G, et al.
(författare)
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Efficient calculations of a large number of highly excited states for multiconfigurational wavefunctions
- 2019
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Ingår i: Journal of Computational Chemistry. - : Wiley. - 0192-8651 .- 1096-987X. ; 40:19, s. 1789-1799
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Tidskriftsartikel (refereegranskat)abstract
- Electronically excited states play important roles in many chemical reactions and spectroscopic techniques. In quantum chemistry, a common technique to solve excited states is the multiroot Davidson algorithm, but it is not designed for processes like X-ray spectroscopy that involves hundreds of highly excited states. We show how the use of a restricted active space wavefunction together with a projection operator to remove low-lying electronic states offers an efficient way to reach single and double-core-hole states. Additionally, several improvements to the stability and efficiency of the configuration interaction (CI) algorithm for a large number of states are suggested. When applied to a series of transition metal complexes the new CI algorithm does not only resolve divergence issues but also leads to typical reduction in computational time by 70%, with the largest savings for small molecules and large active spaces. Together, the projection operator and the improved CI algorithm now make it possible to simulate a wide range of single- and two-photon spectroscopies.
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| 2. |
- Galván, Ignacio Fdez., et al.
(författare)
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OpenMolcas : From Source Code to Insight
- 2019
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Ingår i: Journal of Chemical Theory and Computation. - : American Chemical Society (ACS). - 1549-9618 .- 1549-9626. ; 15:11, s. 5925-5964
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Tidskriftsartikel (refereegranskat)abstract
- In this Article we describe the OpenMolcas environment and invite the computational chemistry community to collaborate. The open-source project already includes a large number of new developments realized during the transition from the commercial MOLCAS product to the open-source platform. The paper initially describes the technical details of the new software development platform. This is followed by brief presentations of many new methods, implementations, and features of the OpenMolcas program suite. These developments include novel wave function methods such as stochastic complete active space self-consistent field, density matrix renormalization group (DMRG) methods, and hybrid multiconfigurational wave function and density functional theory models. Some of these implementations include an array of additional options and functionalities. The paper proceeds and describes developments related to explorations of potential energy surfaces. Here we present methods for the optimization of conical intersections, the simulation of adiabatic and nonadiabatic molecular dynamics, and interfaces to tools for semiclassical and quantum mechanical nuclear dynamics. Furthermore, the Article describes features unique to simulations of spectroscopic and magnetic phenomena such as the exact semiclassical description of the interaction between light and matter, various X-ray processes, magnetic circular dichroism, and properties. Finally, the paper describes a number of built-in and add-on features to support the OpenMolcas platform with postcalculation analysis and visualization, a multiscale simulation option using frozen-density embedding theory, and new electronic and muonic basis sets.
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| 3. |
- Gron, Kurt J., et al.
(författare)
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Nitrogen isotope evidence for manuring of early Neolithic Funnel Beaker Culture cereals from Stensborg, Sweden
- 2017
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Ingår i: Journal of Archaeological Science: Reports. - : Elsevier BV. - 2352-409X. ; 14, s. 575-579
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Tidskriftsartikel (refereegranskat)abstract
- Little is known about arable agriculture in the Early Neolithic (4000–3300 cal BC, Funnel Beaker Culture) of Southern Scandinavia. Archaeobotanical material is rare and few archaeological sites have yielded more than a small number of charred cereal grains. In this short communication, we present single-entity carbon and nitrogen isotope analyses of charred cereals from Stensborg, an early Funnel Beaker Culture site near Stockholm, Sweden. This cereal assemblage is important as it is large, well-preserved and consists of multiple crop species. Our isotopic results indicate that many of the Stensborg cereal crops had been manured and that there is intra- and inter-species variation in manuring. We interpret these data as evidence of an integrated regime of stock-keeping and small-scale agriculture in the early Funnel Beaker Culture near its northernmost limit.
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| 4. |
- Guo, Meiyuan, et al.
(författare)
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Fingerprinting Electronic Structure of Heme Iron by Ab Initio Modeling of Metal L-Edge X-ray Absorption Spectra
- 2019
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Ingår i: Journal of Chemical Theory and Computation. - : American Chemical Society (ACS). - 1549-9618 .- 1549-9626. ; 15:1, s. 477-489
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Tidskriftsartikel (refereegranskat)abstract
- The capability of the multiconfigurational restricted active space approach to identify electronic structure from spectral fingerprints is explored by applying it to iron L-edge X-ray absorption spectroscopy (XAS) of three heme systems that represent the limiting descriptions of iron in the Fe-O-2 bond, ferrous and ferric [Fe(P)(ImH)(2)](0/1+) (P = porphine, ImH = imidazole), and Fe-II(P). The level of agreement between experimental and simulated spectral shapes is calculated using the cosine similarity, which gives a quantitative and unbiased assignment. Further dimensions in fingerprinting are obtained from the L-edge branching ratio, the integrated absorption intensity, and the edge position. The results show how accurate ab initio simulations of metal L-edge XAS can complement calculations of relative energies to identify unknown species in chemical reactions.
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| 5. |
- Guo, Meiyuan, et al.
(författare)
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Molecular orbital simulations of metal 1s2p resonant inelastic X-ray scattering
- 2016
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 120:29, s. 5848-5855
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Tidskriftsartikel (refereegranskat)abstract
- For first-row transition metals, high-resolution 3d electronic structure information can be obtained using resonant inelastic X-ray scattering (RIXS). In the hard X-ray region, a K pre-edge (1s -> 3d) excitation can be followed by monitoring the dipole-allowed K alpha (2p -> 1s) or K beta (3p -> 1s) emission, processes labeled 1s2p or 1s3p RIXS. Here the restricted active space (RAS) approach, which is a molecular orbital method, is used for the first time to study hard X-ray RIXS processes. This is achieved by including the two sets of core orbitals in different partitions of the active space. Transition intensities are calculated using both first- and second-order expansions of the wave vector, including, but not limited to, electric dipoles and quadrupoles. The accuracy of the approach is tested for 1s2p RIXS of iron hexacyanides [Fe(CN)(6)](n-) in ferrous and ferric oxidation states. RAS simulations accurately describe the multiplet structures and the role of 2p and 3d spin-orbit coupling on energies and selection rules. Compared to experiment, relative energies of the two [Fe(CN)(6)](3-) resonances deviate by 0.2 eV in both incident energy and energy transfer directions, and multiplet splittings in [Fe(CN)(6)](4-) are reproduced within 0.1 eV. These values are similar to what can be expected for valence excitations. The development opens the modeling of hard X-ray scattering processes for both solution catalysts and enzymatic systems.
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| 6. |
- Guo, Meiyuan, et al.
(författare)
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Simulations of iron K pre-edge X-ray absorption spectra using the restricted active space method
- 2016
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 4, s. 3250-3259
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Tidskriftsartikel (refereegranskat)abstract
- The intensities and relative energies of metal K pre-edge features are sensitive to both geometric and electronic structures. With the possibility to collect high-resolution spectral data it is important to find theoretical methods that include all important spectral effects: ligand-field splitting, multiplet structures, 3d-4p orbital hybridization, and charge-transfer excitations. Here the restricted active space (RAS) method is used for the first time to calculate metal K pre-edge spectra of open-shell systems, and its performance is tested against on six iron complexes: [FeCl6](n-), [FeCl4](n-), and [Fe(CN)(6)](n-) in ferrous and ferric oxidation states. The method gives good descriptions of the spectral shapes for all six systems. The mean absolute deviation for the relative energies of different peaks is only 0.1 eV. For the two systems that lack centrosymmetry [FeCl4](2-/1-), the ratios between dipole and quadrupole intensity contributions are reproduced with an error of 10%, which leads to good descriptions of the integrated pre-edge intensities. To gain further chemical insight, the origins of the pre-edge features have been analyzed with a chemically intuitive molecular orbital picture that serves as a bridge between the spectra and the electronic structures. The pre-edges contain information about both ligand-field strengths and orbital covalencies, which can be understood by analyzing the RAS wavefunction. The RAS method can thus be used to predict and rationalize the effects of changes in both the oxidation state and ligand environment in a number of hard X-ray studies of small and medium-sized molecular systems.
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| 7. |
- Hahn, Berthold, et al.
(författare)
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Recommended practices for wind farm data collection and reliability assessment for O&M optimization
- 2017
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Ingår i: Energy Procedia. - : Elsevier BV. - 1876-6102. ; 137, s. 358-365
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Konferensbidrag (refereegranskat)abstract
- The paper provides a brief overview of the aims and main results of IEA Wind Task 33. IEA Wind Task 33 was an expert working group with a focus on data collection and reliability assessment for O & M optimization of wind turbines. The working group started in 2012 and finalized the work in 2016. The complete results of IEA Wind Task 33 are described in the expert group report on recommended practices for "Wind farm data collection and reliability assessment for O & M optimization" which will be published by IEA Wind in 2017. This paper briefly presents the background of the work, the recommended process to identify necessary data, and appropriate taxonomies structuring and harmonizing the collected entries. Finally, the paper summarizes the key findings and recommendations from the IEA Wind Task 33 work.
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| 8. |
- Johnstone, Erik V., et al.
(författare)
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Molecular and Electronic Structure of Re2Br4(PMe3)(4)
- 2016
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 55:14, s. 7111-7116
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Tidskriftsartikel (refereegranskat)abstract
- The dinuclear rhenium(II) complex Re2Br4(PMe3)(4) was prepared from the reduction of [Re2Br8](2-) with (n-Bu4N)BH4 in the presence of PMe3 in propanol. The complex was characterized by single-crystal X-ray diffraction (SCXRD) and UV-visible spectroscopy. It crystallizes in the monoclinic C2/c space group and is isostructural with its molybdenum and technetium analogues. The Re-Re distance (2.2521(3) angstrom) is slightly longer than the one in Re2Cl4(PMe3)(4) (2.247(1) angstrom). The molecular and electronic structure of Re2X4(PMe3)(4) (X = Cl, Br) were studied by multiconfigurational quantum chemical methods. The computed ground-state geometry is in excellent agreement with the experimental structure determined by SCXRD. The calculated total bond order (2.75) is consistent with the presence of an electron-rich triple bond and is similar to the one found for Re2Cl4(PMe3)(4). The electronic absorption spectrum of Re2Br4(PMe3)(4) was recorded in benzene and shows a series of low-intensity bands in the range 10 000-26 000 cm(-1). The absorption bands were assigned based on calculations of the excitation energies with the multireference wave functions followed by second-order perturbation theory using the CASSCF/CASPT2 method. Calculations predict that the lowest energy band corresponds to the delta* -> sigma* transition, while the next higher energy bands were attributed to the delta* -> pi*, delta -> sigma*, and delta -> pi* transitions.
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| 9. |
- Khamesian, Marjan, et al.
(författare)
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Spectroscopy of linear and circular polarized light with the exact semiclassical light–matter interaction
- 2019
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Ingår i: Annual Reports in Computational Chemistry. - : Elsevier Ltd. - 1574-1400. - 9780128171196 ; , s. 39-76
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Bokkapitel (refereegranskat)abstract
- We present the theory and the analytical and numerical solution for the calculation of the oscillator and rotatory strengths of molecular systems using a state-specific formalism. For a start, this is done in the context of the exact semiclassical light–matter interaction in association with electronic wave functions expanded in a Gaussian basis. The reader is guided through the standard approximations of the field, e.g., the use of commutators, truncation of Taylor expansions, and the implications of these are discussed in parallel. Expressions for the isotropically averaged values are derived, recovering the isotropic oscillator strength in terms of the transition electric-dipole moment, and the isotropic rotatory strength in terms of the transition electric-dipole and magnetic-dipole moments. This chapter gives a detailed description of the computation of the integrals over the plane wave in association with Gaussian one-particle basis sets. Finally, a brief description is given of how the computed oscillator and rotatory strengths are related to the quantities commonly used and discussed in experimental studies.
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| 10. |
- Larsson, H. R., et al.
(författare)
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Correlation effects in strong-field ionization of heteronuclear diatomic molecules
- 2016
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Ingår i: PHYSICAL REVIEW A. - 2469-9926. ; 93:1
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Tidskriftsartikel (refereegranskat)abstract
- We develop a time-dependent theory to investigate electron dynamics and photoionization processes of diatomic molecules interacting with strong laser fields including electron-electron correlation effects. We combine the recently formulated time-dependent generalized-active-space configuration interaction theory [D. Hochstuhl and M. Bonitz, Phys. Rev. A 86, 053424 (2012); S. Bauch et al., ibid. 90, 062508 (2014)] with a prolate spheroidal basis set including localized orbitals and continuum states to describe the bound electrons and the outgoing photoelectron. As an example, we study the strong-field ionization of the two-center four-electron lithium hydride molecule in different intensity regimes. By using single-cycle pulses, two orientations of the asymmetric heteronuclear molecule are investigated: Li-H, with the electrical field pointing from H to Li, and the opposite case of H-Li. The preferred orientation for ionization is determined and we find a transition from H-Li, for low intensity, to Li-H, for high intensity. The influence of electron correlations is studied at different levels of approximation, and we find a significant change in the preferred orientation. For certain intensity regimes, even an interchange of the preferred configuration is observed, relative to the uncorrelated simulations. Further insight is provided by detailed comparisons of photoelectron angular distributions with and without correlation effects taken into account.
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