Optical properties of pyridine and methyl-pyridinium in water using DFT/MM

Molecular properties such as excitation energies, polarisabilities and two-photon absorption cross-sections of pyridine and N-methyl-pyridinium embedded in a solvent of water are studied using density functional theory/molecular mechanics (DFT/MM) calculations. The purpose of this study is to study how well the differences between a cationic and a neutral specie can be predicted with water as the solvent. In order to answer this question, the DFT/MM method used is benchmarked in terms of convergence profiles, e.g. how many calculations are needed in order to obtain a statistically converged result. Quantification of for example how many water molecules needs to be included in the quantum mechanics system in the calculations before a converged molecular property is obtained which is also benchmarked. The latter will serve as valuable information in further calculations of larger organic molecules, where more experimental data are available. In this work, the calculated excitation energies are compared to experimentally determined ultraviolet/visible (UV/VIS) spectra of both pyridine and N-methyl-pyridinium and a reasonable agreement is found.     

Toward ab initio density functional theory for nuclei

We survey approaches to non-relativistic density functional theory (DFT) for nuclei using progress toward ab initio DFT for Coulomb systems as a guide. Ab initio DFT starts with a microscopic Hamiltonian and is naturally formulated using orbital-based functionals, which generalize the conventional ‘local density plus gradients’ form. The orbitals satisfy single-particle equations with multiplicative (local) potentials. The DFT functionals can be developed starting from internucleon forces using wavefunction-based methods or by Legendre transform via effective actions. We describe known and unresolved issues for applying these formulations to the nuclear many-body problem and discuss how ab initio approaches can help improve empirical energy density functionals.     

Predicting the self-assembled morphology and mechanical properties of mixtures of diblocks and rod-like nanoparticles

We couple a morphological study of a mixture of diblock copolymers and rod-like, solid nanoparticles with a micromechanical simulation to determine how the spatial distribution and aspect ratio of the particles affects the mechanical behavior of the composite. The morphological studies are conducted through the SCF/DFT technique, which couples the self-consist field theory (SCFT) for the diblocks and a density functional theory (DFT) for parallelepiped particles. Through the SCF/DFT calculations, we obtain the equilibrium morphology of the diblock/particle mixtures. We find that the distribution of particles within the polymers is dependent not only on the relative interaction energies between the particles and the different blocks, but also on the aspect ratio of the rod-like solids. The output of the SCF/DFT model serves as the input to the Lattice Spring Model (LSM), which consists of a three-dimensional network of springs. In particular, the location of the different phases is mapped onto the LSM lattice and the appropriate force constants are assigned to the LSM bonds. A stress is applied to the LSM lattice, and we calculate the local stress and strain fields and overall elastic response of the material. We find that high aspect ratio rods can dramatically increase the Young's modulus of the material. By integrating the morphological and mechanical models, we can isolate how modifications in physical characteristics of the particles and diblocks affect both the structure of the mixture and the macroscopic behavior of the composite. Thus, we can establish how choices made in the components affect the ultimate performance of the material.     

Dispersion interactions in density‐functional theory

Density‐functional theory (DFT) allows for the calculation of many chemical properties with relative ease, thus making it extremely useful for the physical organic chemistry community to understand and focus on various experiments. However, density‐functional techniques have their limitations, including the ability to satisfactorily describe dispersion interactions. Given the ubiquitous nature of dispersion in chemical and biological systems, this is not a trivial matter. Recent advances in the development of DFT methods can treat dispersion. These include dispersion‐corrected DFT (using explicit, attractive dispersion terms), parameterized functionals, and dispersion‐correcting potentials, all of which can dramatically improve performance for dispersion‐bound species. In this perspective, we highlight the achievements made in modeling dispersion using DFT. We hope that this will provide valuable insight to both computational chemists and experimentalists, who aim to study physical processes driven by dispersion interactions. Copyright © 2009 John Wiley & Sons, Ltd.     

Symmetry properties of the electron density and following from it limits on the KS-DFT applications

ABSTRACT

At present, the Density Functional Theory (DFT) approach elaborated by Kohn with co-authors more than 50 years ago became the most widely used method for study molecules and solids. Using modern computation facilities, it can be applied to systems with million atoms. In the atmosphere of such great popularity, it is particularly important to know the limits of the applicability of DFT methods. In this report, I will discuss two cases when the conventional DFT approaches, using only electron density ρ and its gradients, cannot be applied (I will not consider the Ψ-versions of DFT). The first case is quite evident. In the degenerated states, the electron density may not be defined, since electronic and nuclear motions cannot be separated, the vibronic interaction mixed them. The second case is related to the spin of the state. As it was rigorously proved by group theoretical methods at the theorem level, the electron density does not depend on the total spin S of the arbitrary N-electron state. It means that the Kohn–Sham equations have the same form for states with different S. The critical survey of elaborated DFT procedures, taking into account spin, shows that they modified only exchange functionals, the correlation functionals do not correspond to the spin of the state. The point is that the conception of spin cannot be defined in the framework of the electron density formalism, which corresponds to the one-particle reduced density matrix. This is the main reason of the problems arising in the study by DFT of magnetic properties of the transition metals. The possible way of resolving these problems can be found in the two-particle reduced density matrix formulation of DFT.     

The spacetime of double field theory: Review,remarks, and outlook

We review double field theory (DFT) with emphasis on the doubled spacetime and its generalized coordinate transformations, which unify diffeomorphisms and b‐field gauge transformations. We illustrate how the composition of generalized coordinate transformations fails to associate. Moreover, in dimensional reduction, the O(d,d) T‐duality transformations of fields can be obtained as generalized diffeomorphisms. Restricted to a half‐dimensional subspace, DFT includes ‘generalized geometry’, but is more general in that local patches of the doubled space may be glued together with generalized coordinate transformations. Indeed, we show that for certain T‐fold backgrounds with non‐geometric fluxes, there are generalized coordinate transformations that induce, as gauge symmetries of DFT, the requisite O(d,d;ℤ) monodromy transformations. Finally we review recent results on the α^′ extension of DFT which, reduced to the half‐dimensional subspace, yields intriguing modifications of the basic structures of generalized geometry.     

The extended Fourier transform for 2D spectral estimation.

We present a linear algebraic method, named the eXtended Fourier Transform (XFT), for spectral estimation from truncated time signals. The method is a hybrid of the discrete Fourier transform (DFT) and the regularized resolvent transform (RRT) (J. Chen et al., J. Magn. Reson. 147, 129-137 (2000)). Namely, it estimates the remainder of a finite DFT by RRT. The RRT estimation corresponds to solution of an ill-conditioned problem, which requires regularization. The regularization depends on a parameter, q, that essentially controls the resolution. By varying q from 0 to infinity one can "tune" the spectrum between a high-resolution spectral estimate and the finite DFT. The optimal value of q is chosen according to how well the data fits the form of a sum of complex sinusoids and, in particular, the signal-to-noise ratio. Both 1D and 2D XFT are presented with applications to experimental NMR signals.     

Atomistic and electronic structure calculation of defects at the surfaces of oxides

We present the results of simulations using both atomistic and density functional theory (DFT) approaches that illustrate the uses of these techniques for investigating the structure and electronic structure of defects at the surfaces of oxides. Atomistic simulation studies of the low index surfaces of spinel (MgAl 2 O 4 ) will show the role of vacancy configuration and surface rearrangement. Atomistic and DFT studies on Li doped MgO illustrate the importance of both the defect structure and its effect of morphology. We will also illustrate using DFT electronic defects at the surface of CeO 2 , which are of great importance in redox reactions and catalytic activity. Finally we will present a novel atomistic approach for predicting the structure of supported oxide nanoclusters giving rise to a wide range of defects including a range of surface terminations, grain formation, mixed screw edge dislocations and misfit dislocations. We will illustrate this using the structure of a BaO supported MgO nanocluster.     

Structure and stability of binary alloy surfaces: Segregation, relaxation, and ordering from first-principles calculations

Although modern computer codes based on density functional theory (DFT) allow the reliable prediction of many surface properties, they often cannot be applied, when the problem of interest demands a consideration of huge configuration spaces or model systems containing many thousand atoms. An important example are binary alloy surfaces where substitutional ordering phenomena on a mesoscopic scale and surface segregation are involved. It will be demonstrated how the combination of first-principle calculations with cluster expansions (CE) and Monte-Carlo (MC) simulations allows for a quantitative prediction of disordered alloy surface properties without any empirical parameters. The concept will be applied to the Pt₂₅Rh₇₅(111) surface. Our results are in excellent agreement with experimental studies. PACS 68.35.-p; 68.35.Md; 61.82.Bg; 71.15.Mb     

On the Coulomb operator for embedded cluster calculations in periodic systems

In performing ab-initio or DFT embedded cluster calculations in infinite periodic systems one unsolved problem is how to embed the quantum cluster in the general case. We show that the Ewald real space sum can be implemented as an operator in the Hamiltonian when the reciprocal space sum is made small.     

Effect of thiophene rings on UV/visible spectra and non‐linear optical (NLO) properties of triphenylamine based dyes: a quantum chemical perspective

In this study, density functional theory (DFT) and time‐dependent DFT (TD‐DFT) theory are use to shed light on how the number of thiophene rings in π‐conjugated system influence the absorption spectra and non‐linear optical (NLO) properties of dyes. The results of theoretical computation show that the absorption spectra are gradually broadened and red‐shifted (384–542 nm) with increasing number of thiophene units. The theoretical examination on non‐linear optical properties was performed on the key parameters of polarizabilty and hyperpolarizability. A remarkable increase in non‐linear optical response was observed on insertion of thiophene rings in π‐spacer. Copyright © 2015 John Wiley & Sons, Ltd.     

Many body effects in the electronic and optical properties of the (1 1 1) surface of diamond

The (1 1 1) face is the cleavage surface of diamond. Understanding its properties is very important for the growing technological interest on the chemistry of diamond surfaces. Within DFT the most stable reconstruction is the Pandey chain model, the atoms on the chain being neither buckled nor dimerised. However this geometry gives rise to a semi metallic band structure in contrast with experimental findings that show the presence of a gap ranging from 0.5 to 2 eV. Here we show that the same equilibrium geometry and thus the same metallic band structure is found relaxing the surface using screened exchange (sX) or Hartree-Fock (HF) functionals. We will discuss in detail how breaking the equivalence of the atoms on the chain affects the band structure and we will show that a buckling would yield a semiconducting surface, but is energetically unfavorable. A semiconducting character can be restored, within the equilibrium geometry, if quasiparticle corrections are carefully included within an iterative GW scheme. The result of the theoretical reflectance anisotropy spectra (RAS) at a DFT-RPA level are also presented and discussed. As expected, a strong anisotropy signal is found at low energies due to transitions between surface states inside the fundamental gap.     

Nonlocal pseudopotentials and magnetic fields

We show how to describe the coupling of electrons to nonuniform magnetic fields in the framework of the widely used norm-conserving pseudopotential approximation for electronic structure calculations. Our derivation applies to magnetic fields that are smooth on the scale of the core region. The method is validated by application to the calculation of the magnetic susceptibility of molecules within density functional theory (DFT) in the local density approximation. Our results are compared with high-quality all-electron DFT results obtained using Gaussian basis sets and another recently proposed pseudopotential formalism.     

A quantum search algorithm of two entangled registers to realize quantum discrete Fouriertransform of signal processing

The discrete Fourier transform （DFT） is the base of modern signal processing. 1-dimensional fast Fourier transform （1D FFT） and 2D FFT have time complexity O（N log N） and O（N^2 log N） respectively. Since 1965, there has been no more essential breakthrough for the design of fast DFT algorithm. DFT has two properties. One property is that DFT is energy conservation transform. The other property is that many DFT coefficients are close to zero. The basic idea of this paper is that the generalized Grover＇s iteration can perform the computation of DFT which acts on the entangled states to search the big DFT coefficients until these big coefficients contain nearly all energy. One-dimensional quantum DFT （1D QDFT） and two-dimensional quantum DFT （2D QDFT） are presented in this paper. The quantum algorithm for convolution estimation is also presented in this paper. Compared with FFT, 1D and 2D QDFT have time complexity O（v/N） and O（N） respectively. QDFT and quantum convolution demonstrate that quantum computation to process classical signal is possible.     

Methane activation on Ni(1 1 1): Effects of poisons and step defects

We have, theoretically and experimentally, investigated the dissociation of methane on the terraces and steps of a Ni(1 1 1) surface. Using Density Functional Theory (DFT) total energy calculations combined with Ultra High Vacuum (UHV) experiments, we find that the steps exhibit a higher activity than the terraces. We have, furthermore, investigated how carbon and sulfur present on the surface will deactivate the steps, leaving only the terraces active. We find the intrinsic sticking probabilities of methane on the steps and terraces at 500 K to be 2.8 × 10⁻⁷ for the steps and 2.1 × 10⁻⁹ for the terraces, in complete agreement with our calculated difference in activation energy of 17 kJ/mol.     

Time-dependent density-functional theory in massively parallel computer architectures: the OCTOPUS project

Octopus is a general-purpose density-functional theory (DFT) code, with a particular emphasis on the time-dependent version of DFT (TDDFT). In this paper we present the ongoing efforts to achieve the parallelization of octopus. We focus on the real-time variant of TDDFT, where the time-dependent Kohn-Sham equations are directly propagated in time. This approach has great potential for execution in massively parallel systems such as modern supercomputers with thousands of processors and graphics processing units (GPUs). For harvesting the potential of conventional supercomputers, the main strategy is a multi-level parallelization scheme that combines the inherent scalability of real-time TDDFT with a real-space grid domain-partitioning approach. A scalable Poisson solver is critical for the efficiency of this scheme. For GPUs, we show how using blocks of Kohn-Sham states provides the required level of data parallelism and that this strategy is also applicable for code optimization on standard processors. Our results show that real-time TDDFT, as implemented in octopus, can be the method of choice for studying the excited states of large molecular systems in modern parallel architectures.     

Generating Tunable Magnetism in AlN Nanoribbons Using Anion/Cation Vacancies:a First-Principles Prediction

Using first-principles approach, we theoretically study the effect of anion/cation vacancies on structural and electro-magnetic properties of zigzag AlN nanoribbons (ZAlNNRs). Calculations were performed using a full spin-polarized method within the density functional theory (DFT). Our findings shed light on how the edge states combined with vacancy engineering can affect electro-magnetic properties of ZAlNNRs. We found that depending on the nature and number of vacancies, ZAlNNRs can design as half-metal or semiconductor. Our results reveal a significant amount of spin magnetic moment for ZAlNNR with Al vacancies (V_Al). These results may open new applications of AlN nano-materials in spintronics.     

极端条件下6Li2O的热力学性能与电子结构

 采用密度泛函理论与准谐振德拜模型研究了面心立方相的⁶Li₂O在极端条件下的热力学性质与电子结构。结果表明: ⁶Li₂O的热膨胀系数在任何温度下都随压强增加明显降低,但仅当压强较低(低于40 GPa)时,温度对6Li2O的热膨胀系数的影响才明显;O原子半径随压强增大而迅速降低,而随温度的变化并不明显;在低压条件下(低于40 GPa),带隙随温度的升高缓慢降低;而在高压条件下(高于40 GPa),温度对带隙宽度的影响几乎可以忽略;无论在什么温度条件下,带隙宽度均随压强的增大而迅速增加。     

Corrections to the density-functional theory electronic spectrum: copper phthalocyanine

A method for improving the electronic spectrum of standard Density-Functional Theory (DFT) calculations (i.e., LDA or GGA approximations) is presented, and its application is discussed for the case of the copper phthalocyanine (CuPc) molecule. The method is based on a treatment of exchange and correlation in a many-body Hamiltonian, and it leads to easy-to-evaluate corrections to the DFT eigenvalues. Self-interaction is largely corrected, so that the modified energy levels do not suffer from spurious crossings, as often encountered for CuPc in DFT, and they remedy the standard underestimation of the gap. As a specific example we study the sequence and position of the CuPc molecular orbitals, which are wrongly calculated by standard DFT, and show that they are correctly reproduced after our corrections are included. The suggested method is fast and simple and, while not as accurate as hybrid or semiempirical functionals for molecular levels, it can be easily applied to any local-orbital DFT approach, improving on several important limitations of standard DFT methods.