International Journal of Quantum Chemistry

Cover image for Vol. 117 Issue 17

Early View (Online Version of Record published before inclusion in an issue)

Impact Factor: 2.92

ISI Journal Citation Reports © Ranking: 2016: 12/100 (Mathematics Interdisciplinary Applications); 12/35 (Physics Atomic Molecular & Chemical); 58/145 (Chemistry Physical)

Online ISSN: 1097-461X

Associated Title(s): Journal of Computational Chemistry


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      Numerical methods for the inverse problem of density functional theory

      Daniel S. Jensen and Adam Wasserman

      Version of Record online: 17 JUL 2017 | DOI: 10.1002/qua.25425

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      The inverse problem of density functional theory (DFT) is often solved in an effort to benchmark and design approximate exchange-correlation potentials. This tutorial describes several numerical inverse-DFT methods with a special focus on convergence. A thorough description of numerical errors is also provided and shown to be essential in designing accurate and efficient inverse-DFT methods.


    1. Quantum reaction dynamics of C(1D) + HD [RIGHTWARDS ARROW] CH(CD) + D(H) on the ground state potential energy surface

      Zhao-Peng Sun, Wen-Kai Zhao and Chuan-Lu Yang

      Version of Record online: 14 JUL 2017 | DOI: 10.1002/qua.25431

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      The reaction between excited carbon atom C(1D) and the hydrogen molecule, or its isotopic variants, plays a significant role in atmospheric and cosmic chemistry. Simulated quantum reaction dynamics of C(1D) + HD displays temperature dependence of initial state-specified rate constants compared with experimental results.


    1. Intermolecular interactions in group 14 hydrides: Beyond C[BOND]H···H[BOND]C contacts

      Jorge Echeverría, Gabriel Aullón and Santiago Alvarez

      Version of Record online: 12 JUL 2017 | DOI: 10.1002/qua.25432

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      E···H (E = Si, Ge, Sn) and H···H short interactions are present in the crystal structures of many group 14 hydrides derivatives. The strength of the interaction increases when descending down the group, and is reinforced by a backbone effect that results in very large dissociation energies for dimers of polymeric molecules.

    2. A theoretical study for the regioselective Diels–Alder reaction of 5,6-fulleroid with strained anti-Bredt olefins

      Naohiko Ikuma

      Version of Record online: 10 JUL 2017 | DOI: 10.1002/qua.25438

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      DFT calculations and activation strain model clarify the higher regioselectivity of anti-Bredt olefin of fulleroid, the 5,6-methylene bridged fullerene derivative. The addition of noncyclic diene at the anti-Bredt olefin shows lower activation energy due to the larger increase of interaction energy than the destabilization of strain energy, while cyclic diene has similar activation energies in both anti-Bredt and another olefin additions.

    3. Density functional evaluation and a feasibility study of intramolecular thione–thiol tautomerization

      Elambalassery G. Jayasree and Soorya Sreedevi

      Version of Record online: 7 JUL 2017 | DOI: 10.1002/qua.25427

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      Thiocarbonyl compounds are fascinating molecules with wide range of biological activities. Different density functionals are benchmarked for geometry and energetics evaluation of such systems and their tautomerization reaction. Hybrid functionals, such as M06-2X and M05-2X, followed by wB97 are found to perform well with basis sets 6-31 + G* and 6-31++G**. Theoretical work is used to investigate the feasibility of tautomerization in three simple and biologically relevant thiocarbonyl systems and in 4′-phosphopantothenoylcysteine decarboxylase catalyzed enzymatic reaction.

    4. The effect of external forces on the initial dissociation of RDX (1,3,5-trinitro-1,3,5-triazine): A mechanochemical study

      Guido Todde, Sanjiv K. Jha and Gopinath Subramanian

      Version of Record online: 7 JUL 2017 | DOI: 10.1002/qua.25426

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      The decomposition reaction of energetic molecules, such as RDX, is often triggered by shock waves or other initiation mechanisms. In this article, the effect of external forces on the three decomposition mechanisms of RDX are studied. The energy barriers and exothermicities of two mechanisms (N[BOND]N fission and concerted mechanism) were significantly influenced by external forces, while the third mechanism (HONO elimination) was influenced to a lesser degree.


    1. The gas phase aldose-ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2-hydroxypropanal and hydroxyacetone

      Jing Sun, Sui So and Gabriel da Silva

      Version of Record online: 6 JUL 2017 | DOI: 10.1002/qua.25434

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      Hydroxycarbonyl compounds can be directly interconverted with a low barrier via a double hydride transfer mechanism. This process explains gas-phase aldose-ketose isomerization in simple sugars and provides new insights into hydroxycarbonyl chemistry in the atmosphere and in the thermochemical processing of carbohydrates.


    1. New structural motif of 18 valence electron molecules with a planar tetracoordinate heavier group 14 center: Unique stabilization effect of a π-type skeleton

      Shuang Yu and Yi-Hong Ding

      Version of Record online: 6 JUL 2017 | DOI: 10.1002/qua.25436

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      First-principles calculations predict the stability of sixteen new planar tetracoordinate Group 14 molecules C2Y2M (Y = Al/Ga/In/T; M = Si/Ge/Sn/Pb), with π-type skeleton. The underlying bonding situation contrasts sharply both with the well-known 18ve-ptC and the limited 18ve-ptM rules, which expect note to little multiple bonding character within the skeleton. Because the YCCY structure is found to stabilize all group 14 atoms in a planar tetracoordinate fashion, the universality of such π-type skeleton is suggested.

    2. Diabatic investigation for the NaRb molecule

      Maha Chaieb, Héla Habli, Leila Mejrissi, Attieh A Al-Ghamdi, Brahim Oujia and Florent Xavier Gadéa

      Version of Record online: 6 JUL 2017 | DOI: 10.1002/qua.25437

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      Cold and ultracold molecules have been the object of considerable interest of late, and understanding their spectroscopic and structural features is a paramount importance for the development of their applications in a wide range of fields. Diabatic representation provides very useful tools for the study of core excitations, for instance, when vibronic interaction is involved. The spectroscopic featured of the polar molecule composed of sodium and rubidium atoms are analyzed by diabatic method.

    3. Impact sensitivity of crystalline phenyl diazonium salts: A first-principles study of solid-state properties determining the phenomenon

      Sergey V. Bondarchuk

      Version of Record online: 6 JUL 2017 | DOI: 10.1002/qua.25430

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      Impact sensitivity is of the most important properties of high-energy density materials (HEDM). Theoretical analysis of solid-state properties allows to safely distinguish sensitive and insensitive HEDMs. Two parameters significantly differ in the case of phenyl diazonium chloride and tetrafluoroborate, namely, the pressure corresponding to zero band gap, so-called, metallization point, and stored energy content. These two quantities together with crystal growth morphology (sphericity of the crystal habit) can serve as criteria of impact sensitivity.

    4. Bandgap engineering of SrTiO3/NaTaO3 heterojunction for visible light photocatalysis

      Guang-Zhao Wang, Hong Chen, Xu-Kai Luo, Hong-Kuan Yuan and An-Long Kuang

      Version of Record online: 6 JUL 2017 | DOI: 10.1002/qua.25424

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      SrTiO3 is a promising photocatalyst, limited in its applicability by the fact it only absorbs in the ultraviolet. The development of SrTiO3/NaTaO3 heterojunction is seen as a promising solution to overcome this limitation. (SrTiO3)5/(NaTaO3)5, (SrTiO3)6/(NaTaO3)6, and (SrTiO3)7/(NaTaO3)7 are, in fact, visible light photocatalysts with potential application for water splitting due to suitable bandgaps and band edge positions with respect to standard hydrogen electrodes.

    5. Uncatalyzed peptide bond formation between two double amino acid molecules in the gas phase

      Marcin Czapla and Sylwia Freza

      Version of Record online: 6 JUL 2017 | DOI: 10.1002/qua.25435

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      The peptide bond formation between the two double amino acid (DAA) systems might undergo via either a concerted (with a single activation barrier connecting the reactants and products) or a stepwise mechanism (with two activation barriers). Computational results indicate that the concerted trans pathway involves lower activation barrier than the concerted cis route. Moreover, the concerted trans mechanism leads directly to the most stable conformer of the DAA-DAA dipeptide.


    1. On the hydrogen atom beyond the Born–Oppenheimer approximation

      Jean Michel Sellier and Kristina G. Kapanova

      Version of Record online: 6 JUL 2017 | DOI: 10.1002/qua.25433

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      Recently a new formulation of quantum mechanics has been suggested, based on the concept of signed particles. The current work applies the new formalism to the time-dependent simulation of a hydrogen atom beyond the Born–Oppenheimer approximation. The hydrogen atom can be considered as a whole quantum two-body problem, through the utilization of the set of three formalism postulates(on the left is depicted the evolution in time of the electron quasi-distribution function).


    1. Theoretical thermodynamic study of the adenine–thymine tautomeric equilibrium: Electronic structure calculations and steered molecular dynamic simulations

      Santiago Tolosa, Jorge Antonio Sansón and Antonio Hidalgo

      Version of Record online: 4 JUL 2017 | DOI: 10.1002/qua.25429

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      Understanding the proton transfer process between the bases that make up DNA pairs is essential because of their involvement in the occurrence of spontaneous mutations in the genetic code. Steered Molecular Dynamics allows for the design of alternative reaction paths for proton exchange and the study of the variation of the free energy in each of them, in addition to describe the microscopic states of the singular points that appear along the reaction path.

    2. First-principles examination of low tolerance factor perovskites

      Sung Gu Kang

      Version of Record online: 27 JUN 2017 | DOI: 10.1002/qua.25420

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      Perovskites are generally formed in the non-polar Pnma phase. First-principles modeling shows how perovskites having a low tolerance factor exhibit ferroelectric instabilities in artificially constrained Pnma phase. A less coordinated A-site environment in low tolerance factor acted critically on the ferroelectric behavior to optimize A-site cation environment by an out-of-plane ferroelectric distortion.

    3. Confinement effects on the electronic structure of M-shell atoms: A study with explicitly correlated wave functions

      Francisco J. Gálvez, Enrique Buendía and Antonio Sarsa

      Version of Record online: 26 JUN 2017 | DOI: 10.1002/qua.25421

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      The effects of pressure on the level scheme of atoms of the M shell are studied. The atom is enclosed in a spherical hard-wall potential and the corresponding Schrödinger equation is solved obtaining the electronic terms under confinement. Electronic correlations are included. Pressure leads to level crossings that are explained in terms of the competition between the 3s, 3p, and 3d orbitals. Confinement changes the filling order of the electronic orbitals modifying the atomic spectrum


    1. The chemical bonding and spectral assignments of rhodium(III)-catalyzed closo-dodecaborate complexes: Ab initio study

      Xiaojun Li, Xiaohui Yang, Hongjiang Ren, Ping Sun and Zhenhua Fang

      Version of Record online: 23 JUN 2017 | DOI: 10.1002/qua.25422

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      The rhodium(III)-catalyzed closo-dodecaborate (RhCD) complex can be stabilized by two H-bridged 3c-2e σ-bonds (B-H-Rh triangles), in which the hybridization of B-2p and Rh-4d states is highlighted, and exhibit the large dissociation energy (5.96 eV) and HOMO–LUMO energy gap (2.90 eV). The theoretical calculations reproduce well the main experimental IR spectrum, and the characteristic peaks are properly assigned.

    2. Magnesium sulfate against oxidative damage of membrane lipids: A theoretical model

      Miguel Fernández, Reinaldo Marín, Fulgencio Proverbio, Delia I. Chiarello and Fernando Ruette

      Version of Record online: 23 JUN 2017 | DOI: 10.1002/qua.25423

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      The role of magnesium sulfate as an inhibitor of lipid peroxidation by free radical is clarified by theoretical analysis. The antioxidant effect of MgSO4 is explained by the formation of contact ion pairs near to the membrane head groups and by OH interactions with Mg+2. The high OH reactivity is diminished after the formation of Mg[BOND]OH bond due to electron spin density redistribution on inline image oxygen atoms. This increases the free radical stability by resonance.


    1. Quantitative investigation of local electric field through absorption spectrum in dye-sensitized solar cells: Atomistic simulations

      Yan Zhang

      Version of Record online: 23 JUN 2017 | DOI: 10.1002/qua.25411

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      Modulated external electric fields are applied to sensitized systems coupling with built-in heterointerfacial electric field, to induce an absorption band shift. The nature of built-in interfacial electric field (e.g., direction vector) can be investigated quantitatively on the basis of the successful establishment of the quantitative relationship between the heterointerfacial electric field and absorption spectrum of adsorbed dye molecule, Stark effect equation.


    1. A hidden rule in metal sulfide fullerenes: A case study of Sc2S@C88

      Zi-Yi Yu, Han Lai, Wen-Juan Zhao, Rui Wu, Xue-Sen Liu and Li-Hua Gan

      Version of Record online: 23 JUN 2017 | DOI: 10.1002/qua.25416

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      Density Functional Theory calculations are used to study the structure and properties of metal sulfide fullerene Sc2S@C88 species, recently detected by mass spectrometry. It is found that the lowest-energy isomers of Sc2S@C88 can transform into each other via direct Stone–Wales rotation, suggesting that “birds of a feather flock together” in metal sulfide fullerenes. This theoretical approach provides a solid tool for the structural identification of metallofullerenes.


    1. Selective separation of strontium by multitopic ion-pair receptor: A DFT exploration

      Biswajit Sadhu, Mahesh Sundararajan, Anilkumar Pillai, Rajvir Singh and Tusar Bandyopadhyay

      Version of Record online: 18 JUN 2017 | DOI: 10.1002/qua.25418

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      Theoretical investigation predicts that K+ selective multitopic ion-pair receptors possess remarkable selectivity for Sr2+ in nitrate media. The structures and preferable binding modes of metal nitrate salts with the ion-pair receptor are studied by means of density functional theory. Based on computed thermodynamic values, two step solvent extraction methodology is proposed for selective separation of chemically alike Ca2+/Sr2+ pair using this receptor.


    1. The influence of noncovalent interactions in metal-free organic dye molecules to augment the efficiency of dye sensitized solar cells: A computational study

      Abul Kalam Biswas, Amitava Das and Bishwajit Ganguly

      Version of Record online: 15 JUN 2017 | DOI: 10.1002/qua.25415

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      The efficiency of dye sensitized solar cells can be enhanced by achieving better planarity of the metal-free organic dye molecules and the thinning of their aggregation on the semiconductor surface. Computed results suggest that designed dyes with phsophazene groups achieve such dual properties.

    2. Carbon–sulfur chains: A high-resolution infrared and quantum-chemical study of C3S and SC7S

      John B. Dudek, Thomas Salomon, Sven Fanghänel and Sven Thorwirth

      Version of Record online: 14 JUN 2017 | DOI: 10.1002/qua.25414

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      Carbon–sulfur clusters are an astronomically relevant class of binary carbon-rich systems whose high-resolution infrared fingerprints have received little attention so far. In the course of the present study, two such clusters, C3S and SC7S, have been investigated through a combination of infrared laser spectroscopy and high-level quantum-chemical calculations. The present study marks the first high-resolution spectroscopic characterization of SC7S.

    3. Dissociation of sulfur oxoacids by two water molecules studied using ab initio and density functional theory calculations

      You Kyoung Chung and Seong Kyu Kim

      Version of Record online: 13 JUN 2017 | DOI: 10.1002/qua.25419

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      H2S2-4O6 species and their hydrated clusters are investigated by means of first-principles approaches. This series of molecules differ by the kind of or the number of atoms connecting two SO3H moieties, which provides variable structural flexibility. All deprotonated conformers form a unique H-bonding network structure, in which H3O+ units are H-bonded to each oxygen atom of two SO3 moieties and the second water molecule, which is in turn H-bonded to one SO3 moiety.

    4. DSD-PBEP86-NL and DOD-PBEP86-NL functionals for noncovalent interactions: Basis set effects and tentative applications to large noncovalent systems

      Feng Yu, Ling-Xiao Fu and Yu Yang

      Version of Record online: 13 JUN 2017 | DOI: 10.1002/qua.25417

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      Double-hybrid density functionals are routinely in use in the study of electronic structure properties of molecules. In particular, the DSD-PBEP86-NL and DOD-PBEP86-NL functionals yield promises for the studies of noncovalent interactions. The basis set effects on these two functionals have been benchmarked. Triple-ζ basis sets, such as cc-pVTZ and def2-TZVPP, with half counterpoise corrections are found to represent the right balance of accuracy and computational cost.


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      Nonadditive kinetic potentials from inverted Kohn–Sham problem

      Mojdeh Banafsheh and Tomasz Adam Wesolowski

      Version of Record online: 12 JUN 2017 | DOI: 10.1002/qua.25410

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      The nonadditive kinetic potential is a key element in density-dependent embedding methods. The correspondence between the ground-state density and the total effective Kohn–Sham potential provides the basis for various methods to construct the nonadditive kinetic potential for any pair of electron densities. Numerical or analytical inversion techniques are sometimes used to this goal, but they apply additional approximations/simplifications.


    1. Reaction mechanism of hydrogen cyanide catalyzed by gas-phase titanium

      Xiaoli Wang, Yongcheng Wang, Shuang Li and Yuwei Zhang

      Version of Record online: 11 JUN 2017 | DOI: 10.1002/qua.25412

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      Computational studies can provide a detailed insight into the reaction of transition metals and hydrogen cyanide. In the case of the Ti atom, the reaction with HCN can go through via four different reaction pathways, each with a specific product distribution. The most favorable mechanism for the reaction is found by means of density functional theory calculations. To obtain the detailed mechanism and kinetic information of Ti with HCN, based on the predictions of the reactive site and reactivity, the possible reaction pathways are discussed one by one. In addition, the bonding properties of main stationary points were analyzed. The results show that there are four reaction pathways, which path b(HCN+Ti[RIGHTWARDS ARROW]IM1[RIGHTWARDS ARROW]TS1[RIGHTWARDS ARROW]IM2[RIGHTWARDS ARROW]T2b[RIGHTWARDS ARROW]IM4) is the most favorable pathway.


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      From charge-transfer excitations to charge-transport phenomena in organic molecular crystals

      Laura Zoppi and Kim K. Baldridge

      Version of Record online: 7 JUN 2017 | DOI: 10.1002/qua.25413

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      Molecular and solid state engineering tools are highlighted as important capabilities toward tailoring new materials with optimal transport properties. Many body electronic structure approaches are seen to be methods of choice for providing predictive insight and guidance to synthetic efforts toward design of improved building blocks. Illustration of these capabilities are demonstrated for prediction of electronic and excitonic properties across a series of investigations involving both planar and curved aromatic compounds.


    1. Mechanisms of DABCO- and DMAP-catalyzed [2 + 4] cycloaddition reactions of methylallenoate with methyleneindolonone: A DFT study

      Yan Li, Tingting Liu and Wenwen Fu

      Version of Record online: 1 JUN 2017 | DOI: 10.1002/qua.25408

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      Lewis bases-promoted annulations of allenoates are one of the most powerful methods for the synthesis of versatile building blocks of biologically active compounds. Studies on such annulations are inherently significant. The reaction mechanism and origin of selectivities in organoamine-catalyzed intermolecular (2 + 4) cycloadditions of methylallenoate and methyleneindolonone have been explored with density functional theory calculations. The role of the catalyst has been studied.

    2. Benchmarking of density functionals for the kinetics and thermodynamics of the hydrolysis of glycosidic bonds catalyzed by glycosidases

      Andreia T. Pereira, António J. M. Ribeiro, Pedro A. Fernandes and Maria J. Ramos

      Version of Record online: 31 MAY 2017 | DOI: 10.1002/qua.25409

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      Despite the large number of density functional (DF) in existence, a universally optimal DF is still missing. DFs performances are dependent on the specific model/reaction/property under study. This work evaluates the performance of DFs, semiempirical, and SCC-DFTB methods for the determination of geometries and the electronic barrier height and energy of reaction of the reactions catalyzed by glycosidases. This will help researchers making appropriate choices in the method selection for computational studies of glycosidase reactions.


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      Quantum chemical design of rotary molecular motors

      Baswanth Oruganti, Jun Wang and Bo Durbeej

      Version of Record online: 12 MAY 2017 | DOI: 10.1002/qua.25405

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      The Nobel Prize in Chemistry 2016 was awarded to Jean-Pierre Sauvage, Sir J. Fraser Stoddart and Bernard L. Feringa “for the design and synthesis of molecular machines.” In this tutorial review, we describe how quantum chemical research over the last few years has provided guidelines and insights for improving the performance of synthetic rotary molecular motors, a type of molecular machines with the ability to convert energy into directed rotary motion.


    1. Performance analysis of open-source distributed file systems for practical large-scale molecular ab initio, density functional theory, and GW + BSE calculations

      Loïc M. Roch, Tyanko Aleksiev, Riccardo Murri and Kim K. Baldridge

      Version of Record online: 5 MAY 2017 | DOI: 10.1002/qua.25392

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      Application of conventional post-Hartree–Fock, density functional, and GW + BSE theories for chemical and biological problems of increasing molecular scale creates an enormous demand for highly efficient storage solutions. In the limitations of the scale-up model, technological progress and continual growth in demand has evolved into solutions that scale-out. Open-source distributed file systems for large-scale molecular calculations are reviewed and performances analyzed and discussed.

    2. Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

      Taye B. Demissie and Kenneth Ruud

      Version of Record online: 5 MAY 2017 | DOI: 10.1002/qua.25393

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      Relativistic two- and four-component density-functional theory is used to demonstrate that the superheavy elements darmstadtium, roentgenium, and copernicium form stable complexes with cyanide, providing new insight into the chemistry of these superheavy elements.


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      Perspective: Coupled cluster theory for atoms and molecules in strong magnetic fields

      Stella Stopkowicz

      Version of Record online: 29 APR 2017 | DOI: 10.1002/qua.25391

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      Coupled cluster (CC) theory is revealed as a powerful tool for theoretical treatment of atoms and molecules in strong magnetic fields. Thus, CC allows accurate prediction and interpretation of astrophysical spectral observations. CC benchmark data is also utilized to assess results from current density functional theory. In the regime around a magnetic field of 1B0 (≈235,000 T), exhibited by white-dwarf stars, chemistry as we know it changes drastically, leading to new mechanisms like perpendicular-paramagnetic bonding.

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      Current development of noncollinear electronic structure theory

      Joshua J. Goings, Franco Egidi and Xiaosong Li

      Version of Record online: 26 APR 2017 | DOI: 10.1002/qua.25398

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      Here, recent developments in noncollinear electronic structure theory are reviewed. Noncollinear wave functions are necessary for studying spin and magnetic phenomena on account of spin-symmetry breaking terms in the Hamiltonian. Recent developments applying noncollinear electronic structure theory to spin and magnetization dynamics, as well as spin-orbit coupling in excited state properties are showcased, and the future of noncollinear electronic structure theory is discussed.


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