Specialized computational chemistry packages have permanently reshaped the landscape of chemical and materials science by providing tools to support and guide experimental efforts and for the prediction of atomistic and electronic properties. In this regard, electronic structure packages have played a special role by using first-principle-driven methodologies to model complex chemical and materials processes. Over the past few decades, the rapid development of computing technologies and the tremendous increase in computational power have offered a unique chance to study complex transformations using sophisticated and predictive many-body techniques that describe correlated behavior of electrons in molecular and condensed phase systems at different levels of theory. In enabling these simulations, novel parallel algorithms have been able to take advantage of computational resources to address the polynomial scaling of electronic structure methods. In this paper, we briefly review the NWChem computational chemistry suite, including its history, design principles, parallel tools, current capabilities, outreach, and outlook.

In the last decade, the quantum chemical version of the density matrix renormalization group (DMRG) method has established itself as the method of choice for calculations of strongly correlated molecular systems. Despite its favourable scaling, it is in practice not suitable for computations of dynamic correlation. We present a novel method for accurate "post-DMRG" treatment of dynamic correlation based on the tailored coupled cluster (CC) theory in which the DMRG method is responsible for the proper description of non-dynamic correlation, whereas dynamic correlation is incorporated through the framework of the CC theory. We illustrate the potential of this method on prominent multireference systems, in particular N2, Cr2 molecules and also oxo-Mn(Salen) for which we have performed the first "post-DMRG" computations in order to shed light on the energy ordering of the lowest spin states.The coupled cluster (CC) approach, introduced to quantum chemistry (QC) by Čížek 1 , is one of the most accurate ab initio methods for the treatment of dynamic electron correlation. The advantages of this scheme include a compact description of the wave function, size-extensivity, invariance to orbital rotations together with a systematic hierarchy of approximations converging towards the full configuration interaction (FCI) limit 2 . Despite the great success of QC and in particular the CC methodology 3 in standard (single-reference) cases, the situation is dramatically different for strongly correlated (multireference) systems 4 , where the usual single-reference approaches become inaccurate or even completely break down. One category of methods designed for the treatment of such systems are multireference coupled cluster (MRCC) approaches, which generalize the CC exponential parameterization of the wave function 5-7 . Out of many formulations of MRCC theories, the class of methods relevant to this work are externally corrected CC, which extract information about the most important higher excitations or active space single and double excitations from an "external" calculation performed by a different method like complete active space self-consistent field (CASSCF) or multireference configuration interaction (MRCI) [8][9][10][11][12][13][14][15][16][17][18][19] . In this letter, we present a further development in this field concerning the tailored CC (TCC) method, where the information for external correction is obtained from a density matrix renormalization group (DMRG) calculation.DMRG is a very powerful approach suitable for treatment of strongly correlated systems originally developed in solid state physics [20][21][22] . The success of DMRG in this field motivated its application to QC problems [23][24][25][26][27][28][29][30][31] where it has proven the potential to outperform traditional QC methods for systems which require very large active spaces, like molecules containing several transition metal atoms 32,33 . Despite the favourable scaling of the DMRG method, it is computationally prohibitive to treat the dynamic cor...

Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin-a mammalian metal transporter-in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

2018): Distributions of vascular plants in the Czech Republic. Part 7. -Preslia 90: 425-531.The seventh part of the series on the distributions of vascular plants in the Czech Republic includes grid maps of 104 taxa in the genera Anthriscus, These maps were produced by taxonomic experts based on examined herbarium specimens, literature and field records. Many of the studied native species are on the national Red List. The genus most affected by decline in abundance is Gentianella, which includes six taxa extirpated from this country and six taxa critically threatened. Another group with a high proportion of endangered species comprises aquatic and wetland plants, which are represented by Callitriche hermaphroditica, Hydrocharis morsusranae, Najas minor, Pseudognaphalium luteoalbum and Stratiotes aloides. Other ecologically specialized groups include mainly montane wetland plants (Epilobium anagallidifolium, E. nutans and Rubus chamaemorus) and plants of rocky habitats (Polypodium interjectum, Trichomanes speciosum and Woodsia ilvensis). The previously rare Woodsia alpina has been extirpated from this country. Alien species mapped in this paper include both archaeophytes and neophytes, mainly from the genera Anthriscus, Cochlearia, Elodea, Epilobium, Hordeum and Phleum. Cochlearia danica, Dittrichia graveolens and Limonium gmelinii have recently colonized habitats along the roads treated by de-icing salt. Senecio inaequidens has also spread mainly along motorways. Epilobium adenocaulon is another successful neophyte; it is now widespread throughout this country and the most successful hybrid parent within the genus. Neophyte aquatics are represented by Egeria densa, Elodea canadensis and E. nuttallii. Spatial distributions and often also temporal dynamics of individual taxa are shown in maps and documented by records included in the Pladias database and available in electronic appendices. The maps are accompanied by comments that include additional information on the distribution, habitats, taxonomy and biology of the taxa. K e y w o r d s:

In this article, we investigate the numerical and theoretical aspects of the coupled-cluster method tailored by matrix-product states. We investigate formal properties of the used method, such as energy size consistency and the equivalence of linked and unlinked formulation. The existing mathematical analysis is here elaborated in a quantum chemical framework. In particular, we highlight the use of what we have defined as a complete active space-external space gap describing the basis splitting between the complete active space and the external part generalizing the concept of a HOMO−LUMO gap. Furthermore, the behavior of the energy error for an optimal basis splitting, i.e., an active space choice minimizing the density matrix renormalization group-tailored coupled-cluster singles doubles error, is discussed. We show numerical investigations on the robustness with respect to the bond dimensions of the single orbital entropy and the mutual information, which are quantities that are used to choose a complete active space. Moreover, the dependence of the groundstate energy error on the complete active space has been analyzed numerically in order to find an optimal split between the complete active space and external space by minimizing the density matrix renormalization group-tailored coupled-cluster error.

The ability to engineer geometrically well-defined antidots in large triangulene homologues allows for creating an entire family of triangulene quantum rings (TQRs) with tunable high-spin ground state, crucial for nextgeneration molecular spintronic devices. Herein, we report the synthesis of an open-shell [7]triangulene quantum ring ([7]TQR) molecule on Au(111) through the surface-assisted cyclodehydrogenation of a rationally designed kekulene derivative. Bond-resolved scanning tunneling microscopy (BR-STM) unambiguously imaged the molecular backbone of a single [7]TQR with a triangular zigzag edge topology, which can be viewed as [7]triangulene decorated with a coronenelike antidot in the center. Additionally, dI/dV mapping reveals that both inner and outer zigzag edges contribute to the edge-localized and spin-polarized electronic states of [7]TQR. Both experimental results and spin-polarized density functional theory calculations indicate that [7]TQR retains its open-shell septuple ground state (S = 3) on Au(111). This work demonstrates a new route for the design of high-spin graphene quantum rings for future quantum devices.

Polycyclic aromatic hydrocarbons (PAHs) are a family of organic compounds comprising two or more fused aromatic rings which feature manifold applications in modern technology. Among these species, those presenting an open-shell magnetic ground state are of particular interest for organic electronic, spintronic, and non-linear optics and energy storage devices. Within PAHs, special attention has been devoted in recent years to the synthesis and study of the acene and fused acene (periacene) families, steered by their decreasing HOMO–LUMO gap with length and predicted open-shell character above some size. However, an experimental fingerprint of such magnetic ground state has remained elusive. Here, we report on the in-depth electronic characterization of isolated peripentacene molecules on a Au(111) surface. Scanning tunnelling spectroscopy, complemented by computational investigations, reveals an antiferromagnetic singlet ground state, characterized by singlet–triplet inelastic excitations with an experimental effective exchange coupling (J eff) of 40.5 meV. Our results deepen the fundamental understanding of organic compounds with magnetic ground states, featuring perspectives in carbon-based spintronic devices.

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