scholarly journals Novel Density Functional Methodology for the Computation of Accurate Electronic and Thermodynamic Properties of Molecular Systems and Improved Long-Range Behavior

1998 ◽  
Vol 102 (50) ◽  
pp. 10442-10442
Author(s):  
Sherif A. Kafafi
Keyword(s):  
Thermodynamic Properties ◽  
Long Range ◽  
Density Functional ◽  
Molecular Systems

Computational Investigation of the Asymmetry in Photosynthetic Reaction Center Models from First Principles

2020 ◽  
Author(s):  
Denis Artiukhin ◽  
Patrick Eschenbach ◽  
Johannes Neugebauer
Keyword(s):  
Spin Density ◽  
Reaction Center ◽  
Density Functional ◽  
Photosynthetic Reaction Center ◽  
Chem Phys ◽  
Molecular Structures ◽  
Error Characteristic ◽  
Molecular Systems ◽  
Density Distributions ◽  
The Asymmetry

We present a computational analysis of the asymmetry in reaction center models of photosystem I, photosystem II, and bacteria from <i>Synechococcus elongatus</i>, <i>Thermococcus vulcanus</i>, and <i>Rhodobacter sphaeroides</i>, respectively. The recently developed FDE-diab methodology [J. Chem. Phys., 148 (2018), 214104] allowed us to effectively avoid the spin-density overdelocalization error characteristic for standard Kohn–Sham Density Functional Theory and to reliably calculate spin-density distributions and electronic couplings for a number of molecular systems ranging from dimeric models in vacuum to large protein including up to about 2000 atoms. The calculated spin densities showed a good agreement with available experimental results and were used to validate reaction center models reported in the literature. We demonstrated that the applied theoretical approach is very sensitive to changes in molecular structures and relative orientation of molecules. This makes FDE-diab a valuable tool for electronic structure calculations of large photosynthetic models effectively complementing the existing experimental techniques.

scholarly journals Weak Interactions in Cocrystals of Isoniazid with Glycolic and Mandelic Acids

Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 328
Author(s):  
Raquel Álvarez-Vidaurre ◽  
Alfonso Castiñeiras ◽  
Antonio Frontera ◽  
Isabel García-Santos ◽  
Diego M. Gil ◽  
...  
Keyword(s):  
Density Functional ◽  
Glycolic Acid ◽  
Weak Interactions ◽  
Three Dimensional ◽  
Functional Theory ◽  
Molecular Systems ◽  
X Ray Crystallography ◽  
Hydroxycarboxylic Acids ◽  
Non Covalent Interactions ◽  
Covalent Interactions

This work deals with the preparation of pyridine-3-carbohydrazide (isoniazid, inh) cocrystals with two α-hydroxycarboxylic acids. The interaction of glycolic acid (H2ga) or d,l-mandelic acid (H2ma) resulted in the formation of cocrystals or salts of composition (inh)·(H2ga) (1) and [Hinh]+[Hma]–·(H2ma) (2) when reacted with isoniazid. An N′-(propan-2-ylidene)isonicotinic hydrazide hemihydrate, (pinh)·1/2(H2O) (3), was also prepared by condensation of isoniazid with acetone in the presence of glycolic acid. These prepared compounds were well characterized by elemental analysis, and spectroscopic methods, and their three-dimensional molecular structure was determined by single crystal X-ray crystallography. Hydrogen bonds involving the carboxylic acid occur consistently with the pyridine ring N atom of the isoniazid and its derivatives. The remaining hydrogen-bonding sites on the isoniazid backbone vary based on the steric influences of the derivative group. These are contrasted in each of the molecular systems. Finally, Hirshfeld surface analysis and Density-functional theory (DFT) calculations (including NCIplot and QTAIM analyses) have been performed to further characterize and rationalize the non-covalent interactions.

scholarly journals Comparison of the Performances of Different Computational Methods to Calculate the Electrochemical Stability of Selected Ionic Liquids

Materials ◽  
2021 ◽  
Vol 14 (12) ◽  
pp. 3221
Author(s):  
Annalisa Paolone ◽  
Sergio Brutti
Keyword(s):  
Ionic Liquids ◽  
Density Functional ◽  
Quantitative Agreement ◽  
Electrochemical Stability ◽  
Functional Theory ◽  
Molecular Systems ◽  
Reduction Potentials ◽  
Adiabatic Transitions ◽  
Alkyl Ammonium ◽  
Transition Scheme

The electrochemical stability windows (ESW) of selected ionic liquids have been calculated by comparing different computational approaches previously suggested in the literature. The molecular systems under study are based on di-alkyl imidazolium and tetra-alkyl ammonium cations coupled with two different imide anions (namely, bis-fluorosulfonyl imide and bis-trifluoromethyl sulfonyl imide), for which an experimental investigation of the ESW is available. Thermodynamic oxidation and reduction potentials have here been estimated by different models based on calculations either on single ions or on ionic couples. Various Density Functional Theory (DFT) functionals (MP2, B3LYP, B3LYP including a polarizable medium and empirical dispersion forces) were exploited. Both vertical and adiabatic transitions between the starting states and the oxidized or reduced states were considered. The approach based on calculations on ionic couples is not able to reproduce the experimental data, whatever the used DFT functional. The best quantitative agreement is obtained by calculations on single ions when the MP2 functional in vacuum is considered and the transitions between differently charged states are vertical (purely electronic without the relaxation of the structure). The B3LYP functional underestimates the ESW. The inclusion of a polar medium excessively widens the ESW, while a large shrinkage of the ESW is obtained by adopting an adiabatic transition scheme instead of a vertical transition one.

scholarly journals Quasi-1D XY antiferromagnet Sr2Ni(SeO3)2Cl2 at Sakai-Takahashi phase diagram

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
E. S. Kozlyakova ◽  
A. V. Moskin ◽  
P. S. Berdonosov ◽  
V. V. Gapontsev ◽  
S. V. Streltsov ◽  
...  
Keyword(s):  
Phase Diagram ◽  
Long Range ◽  
Density Functional ◽  
Uniaxial Anisotropy ◽  
Exchange Interactions ◽  
Spin Liquid ◽  
Functional Theory ◽  
One Dimensional ◽  
Ordered Phases ◽  
Experimental Findings

AbstractUniform quasi-one-dimensional integer spin compounds are of interest as a potential realization of the Haldane conjecture of a gapped spin liquid. This phase, however, has to compete with magnetic anisotropy and long-range ordered phases, the implementation of which depends on the ratio of interchain J′ and intrachain J exchange interactions and both uniaxial D and rhombic E single-ion anisotropies. Strontium nickel selenite chloride, Sr2Ni(SeO3)2Cl2, is a spin-1 chain system which passes through a correlations regime at Tmax ~ 12 K to long-range order at TN = 6 K. Under external magnetic field it experiences the sequence of spin-flop at Bc1 = 9.0 T and spin-flip transitions Bc2 = 23.7 T prior to full saturation at Bsat = 31.0 T. Density functional theory provides values of the main exchange interactions and uniaxial anisotropy which corroborate the experimental findings. The values of J′/J = 0.083 and D/J = 0.357 place this compound into a hitherto unoccupied sector of the Sakai-Takahashi phase diagram.

scholarly journals First-Principles Study of Mechanical and Thermodynamic Properties of Binary and Ternary CoX (X = W and Mo) Intermetallic Compounds

Materials ◽  
2021 ◽  
Vol 14 (6) ◽  
pp. 1404
Author(s):  
Yunfei Yang ◽  
Changhao Wang ◽  
Junhao Sun ◽  
Shilei Li ◽  
Wei Liu ◽  
...  
Keyword(s):  
Free Energy ◽  
Thermodynamic Properties ◽  
Gibbs Free Energy ◽  
Density Functional ◽  
Vibrational Entropy ◽  
Functional Theory ◽  
Lattice Constants ◽  
The Density Functional Theory ◽  
Ductile Behavior ◽  
Pseudo Potential

In this study, the structural, elastic, and thermodynamic properties of DO19 and L12 structured Co3X (X = W, Mo or both W and Mo) and μ structured Co7X6 were investigated using the density functional theory implemented in the pseudo-potential plane wave. The obtained lattice constants were observed to be in good agreement with the available experimental data. With respect to the calculated mechanical properties and Poisson’s ratio, the DO19-Co3X, L12-Co3X, and μ-Co7X6 compounds were noted to be mechanically stable and possessed an optimal ductile behavior; however, L12-Co3X exhibited higher strength and brittleness than DO19-Co3X. Moreover, the quasi-harmonic Debye–Grüneisen approach was confirmed to be valid in describing the temperature-dependent thermodynamic properties of the Co3X and Co7X6 compounds, including heat capacity, vibrational entropy, and Gibbs free energy. Based on the calculated Gibbs free energy of DO19-Co3X and L12-Co7X6, the phase transformation temperatures for DO19-Co3X to L12-Co7X6 were determined and obtained values were noted to match well with the experiment results.

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