Sergey V. Levchenko

Equation-of-motion spin-flip coupled-cluster model with single and double substitutions: Theory and application to cyclobutadiene

While the equation-of-motion coupled-cluster (EOM-CC) method is capable of describing certain multiconfigurational wave functions within a single-reference framework (e.g., open-shell type excited states, doublet radicals, etc.), it may fail in cases of more extensive degeneracy, e.g., bond breaking and polyradicals. This work presents an extension of the EOM-CC approach to these chemically important situations. In our approach, target multiconfigurational wave functions are described as spin-flipping excitations from the high-spin reference state. This enables a balanced treatment of nearly degenerate electronic configurations present in the target low-spin wave functions. The relations between the traditional spin-conserving EOM models and the EOM spin-flip method is discussed. The presentation of the formalism emphasizes the variational properties of the theory and shows that the killer condition is rigorously satisfied in single-reference EOM-CC theories. The capabilities and advantages of the new approach are demonstrated by its application to cyclobutadiene.

Big Data of Materials Science: Critical Role of the Descriptor

Statistical learning of materials properties or functions so far starts with a largely silent, nonchallenged step: the choice of the set of descriptive parameters (termed descriptor). However, when the scientific connection between the descriptor and the actuating mechanisms is unclear, the causality of the learned descriptor-property relation is uncertain. Thus, a trustful prediction of new promising materials, identification of anomalies, and scientific advancement are doubtful. We analyze this issue and define requirements for a suitable descriptor. For a classic example, the energy difference of zinc blende or wurtzite and rocksalt semiconductors, we demonstrate how a meaningful descriptor can be found systematically.

A Critical Assessment of Li/MgO-Based Catalysts for the Oxidative Coupling of Methane

Li/MgO is one of the most frequently investigated catalysts for the oxidative coupling of methane. Besides catalytic testing, it is also a suitable system to perform surface science experiments and quantum chemical calculations, which is not possible for many other active catalysts. However, the real structure of Li/MgO, the nature of the active center and the structure - activity relationship remain unclear, despite all the research that has been done. The aim of this review is to summarize the available knowledge on Li/MgO to structure and accelerate and improve the ongoing work on this catalytic system.

Many-Body Dispersion Interactions in Molecular Crystal Polymorphism

Polymorphs of molecular crystals are often very close in energy, yet they may possess very different physical and chemical properties. The understanding of polymorphism is therefore of great importance for a variety of applications, ranging from drug design to nonlinear optics and hydrogen storage. While the crystal structure prediction blind tests conducted by the Cambridge Crystallographic Data Centre have shown steady progress toward reliable structure prediction for molecular crystals, several challenges remain, including molecular salts, hydrates, and flexible molecules with several stable conformers. The ability to identify and rank all of the relevant polymorphs of a given molecular crystal hinges on an accurate description of their relative energetic stability. Hence, a first-principles quantum mechanical method that can attain the required accuracy of around 0.1–0.2 kcalmol 1 would clearly be an indispensable tool for polymorph prediction. In this work, we show that accounting for the nonadditive many-body dispersion (MBD) energy beyond the standard pairwise approximation is crucial for the correct qualitative and quantitative description of polymorphism in molecular crystals. We demonstrate this through three fundamental and stringent benchmark examples: glycine, oxalic acid, and tetrolic acid. These systems represent a broad class of molecular crystals, comprising hydrogenbonded (H-bonded) networks of amino acids and carboxylic acids. Among the first-principles methods, density functional theory (DFT) is the most widely used approach in the study of polymorphism in molecular crystals. However, most common exchange-correlation functionals (including hybrid functionals) are based on semi-local electron correlation, and thereby fail to capture the contribution of dispersion interactions to the stability of molecular crystals. These ubiquitous noncovalent interactions are quantum mechanical in nature and correspond to the multipole moments induced in response to instantaneous fluctuations in the electron density. To incorporate these long-range electron correlation effects within DFT, significant progress has been made by using the standard C6/R 6 pairwise additive expression for the dispersion energy. Indeed, DFT with pairwise dispersion terms can yield accurate results when the energy differences between molecular crystal polymorphs are sufficiently large. Notably, Neumann et al. have achieved the highest success rate in the last two blind tests using such methods. However, these pairwise dispersion approaches, even when used in conjunction with state-of-the-art functionals, are still unable to reach the level of accuracy required to describe polymorphism in many relevant molecular crystals, including glycine and oxalic acid. Recently, a novel and efficient method for describing the many-body dispersion (MBD) energy has been developed, building upon the Tkatchenko–Scheffler (TS) pairwise method. Within the TS approach, the effective dispersion coefficients (C6) are calculated from the DFTelectron density, hence the effect of the local environment of an atom in a molecule is accurately accounted for by construction. The MBD method presents a two-fold improvement over the TS approach by including: 1) the long-range electrodynamic screening through the self-consistent solution of the dipole– dipole electric-field coupling equations for the effective polarizability, and 2) the non-pairwise-additive many-body dispersion energy to infinite order through diagonalization of the Hamiltonian corresponding to a system of coupled fluctuating dipoles. The inclusion of the MBD energy in DFT leads to a significant improvement in the binding energies between organic molecules, and for the cohesion of the benzene and oligoacene molecular crystals. The MBD energy, like the TS energy, can be added to any DFT functional, requiring only the adjustment of a single rangeseparation parameter per functional. [*] N. Marom, J. R. Chelikowsky Center for Computational Materials Institute for Computational Engineering and Sciences The University of Texas at Austin Austin, TX 78712 (USA) E-mail: noa@ices.utexas.edu

Temperature‐Dependent Morphology, Magnetic and Optical Properties of Li‐Doped MgO

Li‐doped MgO is a potential catalyst for the oxidative coupling of methane, whereby surface Li+ O− centers are suggested to be the chemically active species. To elucidate the role of Li in the MgO matrix, two model systems are prepared and their morphological, optical and magnetic properties as a function of Li doping are investigated. The first is an MgO film deposited on Mo(001) and doped with various amounts of Li, whereas the second is a powder sample fabricated by calcination of Li and Mg precursors in an oxygen atmosphere. Scanning tunneling and transmission electron microscopy are performed to characterize the morphology of both samples. At temperatures above 700 K, Li starts segregating towards the surface and forms irregular Li‐rich oxide patches. Above 1050 K, Li desorbs from the MgO surface, leaving behind a characteristic defect pattern. Traces of Li also dissolve into the MgO, as concluded from a distinct optical signature that is absent in the pristine oxide. No electron paramagnetic resonance signal that would be compatible with Li+O− centers is detected in the two Li/MgO samples. Density‐functional theory calculations are used to determine the thermodynamic stability of various Li‐induced defects in the MgO. The calculations clarify the driving forces for Li segregation towards the MgO surface, but also rationalize the absence of Li+O− centers. From the combination of experimental and theoretical results, a detailed picture arises on the role of Li for the MgO properties, which can be used as a starting point to analyze the chemical behavior of the doped oxide in future.

Analytic gradients for the spin-conserving and spin-flipping equation-of-motion coupled-cluster models with single and double substitutions

Analytic gradient expressions for the spin-conserving and spin-flipping equation-of-motion coupled-cluster models with single and double substitutions are derived using a Lagrangian approach for the restricted and unrestricted Hartree-Fock references, both for the case of all orbitals being active in correlated calculations and for the frozen core and/or virtual orbitals. Details of the implementation within the Q-CHEM electronic structure package are discussed. The capabilities of the new code are demonstrated by application to cyclobutadiene.

Stability and metastability of clusters in a reactive atmosphere: Theoretical evidence for unexpected stoichiometries of MgMOx

By applying a genetic algorithm and ab initio atomistic thermodynamics, we identify the stable and metastable compositions and structures of MgMOx clusters at realistic temperatures and oxygen pressures. We find that small clusters (M≲5) are in thermodynamic equilibrium when x>M. The nonstoichiometric clusters exhibit peculiar magnetic behavior, suggesting the possibility of tuning magnetic properties by changing environmental pressure and temperature conditions. Furthermore, we show that density-functional theory with a hybrid exchange-correlation functional is needed for predicting accurate phase diagrams of metal-oxide clusters. Neither a (sophisticated) force field nor density-functional theory with (semi)local exchange-correlation functionals is sufficient for even a qualitative prediction.

Photodissociation dynamics of the NO dimer. I. Theoretical overview of the ultraviolet singlet excited states

Molecular orbital theory and calculations are used to describe the ultraviolet singlet excited states of NO dimer. Qualitatively, we derive and catalog the dimer states by correlating them with monomer states, and provide illustrative complete active space self-consistent field calculations. Quantitatively, we provide computational estimates of vertical transition energies and absorption intensities with multireference configuration interaction and equations-of-motion coupled-cluster methods, and examine an important avoided crossing between a Rydberg and a valence state along the intermonomer and intramonomer stretching coordinates. The calculations are challenging, due to the high density of electronic states of various types (valence and Rydberg, excimer and charge transfer) in the 6-8 eV region, and the multiconfigurational nature of the ground state. We have identified a bright charge-transfer (charge-resonance) state as responsible for the broadband seen in UV absorption experiments. We also use our results to facilitate the interpretation of UV photodissociation experiments, including the time-resolved 6 eV photodissociation experiments to be presented in the next two papers of this series.

Rigorous definition of oxidation states of ions in solids.

We present justification and a rigorous procedure for electron partitioning among atoms in extended systems. The method is based on wave-function topology and the modern theory of polarization, rather than charge density partitioning or wave-function projection, and, as such, reformulates the concept of oxidation state without assuming real-space charge transfer between atoms. This formulation provides rigorous electrostatics of finite-extent solids, including films and nanowires.

Learning physical descriptors for materials science by compressed sensing

The availability of big data in materials science offers new routes for analyzing materials properties and functions and achieving scientific understanding. Finding structure in these data that is not directly visible by standard tools and exploitation of the scientific information requires new and dedicated methodology based on approaches from statistical learning, compressed sensing, and other recent methods from applied mathematics, computer science, statistics, signal processing, and information science. In this paper, we explain and demonstrate a compressed-sensing based methodology for feature selection, specifically for discovering physical descriptors, i.e., physical parameters that describe the material and its properties of interest, and associated equations that explicitly and quantitatively describe those relevant properties. As showcase application and proof of concept, we describe how to build a physical model for the quantitative prediction of the crystal structure of binary compound semiconductors.