Density Functional
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2022 ◽  
Vol 5 (1) ◽  
Ole Bunjes ◽  
Lucas A. Paul ◽  
Xinyue Dai ◽  
Hongyan Jiang ◽  
Tobias Claus ◽  

AbstractAtomic scale studies of the anchoring of catalytically active complexes to surfaces may provide valuable insights for the design of new catalytically active hybrid systems. In this work, the self-assembly of 1D, 2D and 3D structures of the complex fac-Re(bpy)(CO)3Cl (bpy = 2,2′-bipyridine), a CO2 reduction catalyst, on the Ag(001) surface are studied by a combination of low-temperature scanning tunneling microscopy and density functional theory calculations. Infrared and sum frequency generation spectroscopy confirm that the complex remains chemically intact under sublimation. Deposition of the complexes onto the silver surface at 300 K leads to strong local variations in the resulting surface coverage on the nanometer scale, indicating that in the initial phase of deposition a large fraction of the molecules is desorbing from the surface. Low coverage regions show a decoration of step edges aligned along the crystal’s symmetry axes <110>. These crystallographic directions are found to be of major importance to the binding of the complexes to the surface. Moreover, the interaction between the molecules and the substrate promotes the restructuring of surface steps along these directions. Well-aligned and decorated steps are found to act as nucleation point for monolayer growth (2D) before 3D growth starts.

2022 ◽  
Vol 13 (1) ◽  
Xueli Li ◽  
Zhonghua Xiang

AbstractThe atomic configurations of FeNx moieties are the key to affect the activity of oxygen rection reaction (ORR). However, the traditional synthesis relying on high-temperature pyrolysis towards combining sources of Fe, N, and C often results in the plurality of local environments for the FeNx sites. Unveiling the effect of carbon matrix adjacent to FeNx sites towards ORR activity is important but still is a great challenge due to inevitable connection of diverse N as well as random defects. Here, we report a proof-of-concept study on the evaluation of covalent-bonded carbon environment connected to FeN4 sites on their catalytic activity via pyrolysis-free approach. Basing on the closed π conjugated phthalocyanine-based intrinsic covalent organic polymers (COPs) with well-designed structures, we directly synthesized a series of atomically dispersed Fe-N-C catalysts with various pure carbon environments connected to the same FeN4 sites. Experiments combined with density functional theory demonstrates that the catalytic activities of these COPs materials appear a volcano plot with the increasement of delocalized π electrons in their carbon matrix. The delocalized π electrons changed anti-bonding d-state energy level of the single FeN4 moieties, hence tailored the adsorption between active centers and oxygen intermediates and altered the rate-determining step.

2022 ◽  
Vol 13 (1) ◽  
Masaya Nakajima ◽  
Yusuke Adachi ◽  
Tetsuhiro Nemoto

AbstractAlthough computational simulation-based natural product syntheses are in their initial stages of development, this concept can potentially become an indispensable resource in the field of organic synthesis. Herein we report the asymmetric total syntheses of several resveratrol dimers based on a comprehensive computational simulation of their biosynthetic pathways. Density functional theory (DFT) calculations suggested inconsistencies in the biosynthesis of vaticahainol A and B that predicted the requirement of structural corrections of these natural products. According to the computational predictions, total syntheses were examined and the correct structures of vaticahainol A and B were confirmed. The established synthetic route was applied to the asymmetric total synthesis of (−)-malibatol A, (−)-vaticahainol B, (+)-vaticahainol A, (+)-vaticahainol C, and (−)-albiraminol B, which provided new insight into the biosynthetic pathway of resveratrol dimers. This study demonstrated that computation-guided organic synthesis can be a powerful strategy to advance the chemical research of natural products.

2022 ◽  
Vol 13 (1) ◽  
Yan Shao ◽  
Wei Gao ◽  
Hejin Yan ◽  
Runlai Li ◽  
Ibrahim Abdelwahab ◽  

AbstractMolecularly soft organic-inorganic hybrid perovskites are susceptible to dynamic instabilities of the lattice called octahedral tilt, which directly impacts their carrier transport and exciton-phonon coupling. Although the structural phase transitions associated with octahedral tilt has been extensively studied in 3D hybrid halide perovskites, its impact in hybrid 2D perovskites is not well understood. Here, we used scanning tunneling microscopy (STM) to directly visualize surface octahedral tilt in freshly exfoliated 2D Ruddlesden-Popper perovskites (RPPs) across the homologous series, whereby the steric hindrance imposed by long organic cations is unlocked by exfoliation. The experimentally determined octahedral tilts from n = 1 to n = 4 RPPs from STM images are found to agree very well with out-of-plane surface octahedral tilts predicted by density functional theory calculations. The surface-enhanced octahedral tilt is correlated to excitonic redshift observed in photoluminescence (PL), and it enhances inversion asymmetry normal to the direction of quantum well and promotes Rashba spin splitting for n > 1.

2022 ◽  
Vol 11 ◽  
Meilin Mu ◽  
Hongwei Gao

The geometric structure of azido Pt(IV) compounds containing picoline was calculated by using density functional theory(DFT) at the LSDA/SDD level. The ESP distribution shows the possible reaction sites of the compounds. In addition, the frequency calculation results assigned the infrared spectra of these compounds, and specified important stretching and bending vibrations. The HOMO-LUMO energy gaps of these compounds are also calculated to explain the charge transfer of the molecules. The distribution of Mulliken charges and natural atomic charges of these atoms is also calculated. Natural bond orbital(NBO) analysis explains the intramolecular interactions and their electron density.

2022 ◽  
Vol 13 (1) ◽  
Xiaoting Chen ◽  
Laura P. Granda-Marulanda ◽  
Ian T. McCrum ◽  
Marc T. M. Koper

AbstractDevelopment of reversible and stable catalysts for the electrochemical reduction of CO2 is of great interest. Here, we elucidate the atomistic details of how a palladium electrocatalyst inhibits CO poisoning during both formic acid oxidation to carbon dioxide and carbon dioxide reduction to formic acid. We compare results obtained with a platinum single-crystal electrode modified with and without a single monolayer of palladium. We combine (high-scan-rate) cyclic voltammetry with density functional theory to explain the absence of CO poisoning on the palladium-modified electrode. We show how the high formate coverage on the palladium-modified electrode protects the surface from poisoning during formic acid oxidation, and how the adsorption of CO precursor dictates the delayed poisoning during CO2 reduction. The nature of the hydrogen adsorbed on the palladium-modified electrode is considerably different from platinum, supporting a model to explain the reversibility of this reaction. Our results help in designing catalysts for which CO poisoning needs to be avoided.

2022 ◽  
Vol 112 (1) ◽  
Kati Finzel

AbstractThe bifunctional formalism presents an alternative how to obtain the functional value from its functional derivative by exploiting homogeneous density scaling. In the bifunctional formalism the density dependence of the functional derivative is suppressed. Consequently, those derivatives have to be treated as formal functional derivatives. For a pointwise correspondence between the true and the formal functional derivative, the bifunctional expression yields the same value as the density functional. Within the bifunctional formalism the functional value can directly be obtained from its derivative (while the functional itself remains unknown). Since functional derivatives are up to a constant uniquely defined, this approach allows for a pointwise comparison between approximate potentials and reference potentials. This aspect is especially important in the field of orbital-free density functional theory, where the burden is to approximate the kinetic energy. Since in the bifunctional approach the potential is approximated directly, full control is given over the latter, and consequently over the final electron densities obtained from variational procedure. Besides the bifunctional formalism itself another concept is introduced, dividing the total non-interacting kinetic energy into a known functional part and a remainder, called Pauli kinetic energy. Only the remainder requires further approximations. For practical purposes sufficiently accurate Pauli potentials for application on atoms, molecular and solid-state systems are presented.

Membranes ◽  
2022 ◽  
Vol 12 (1) ◽  
pp. 77
Guangjun Chen ◽  
Lei Gan ◽  
Huihui Xiong ◽  
Haihui Zhang

Designing a high-performance gas sensor to efficiently detect the hazardous NH3 molecule is beneficial to air monitoring and pollution control. In this work, the first-principles calculations were employed to investigate the adsorption structures, electronic characteristics, and gas sensing properties of the pristine and B-, N-, P-, Al-, and Si-doped penta-graphene (PG) toward the NH3, H2S, and SO2 molecules. The results indicate that the pristine PG is insensitive to those toxic gases due to the weak adsorption strength and long adsorption distance. Nevertheless, the doping of B, N, Al, and Si (B and Al) results in the transition of NH3 (H2S and SO2) adsorption from physisorption to chemisorption, which is primarily ascribed to the large charge transfer and strong orbital hybridizations between gas molecules and doping atoms. In addition, NH3 adsorption leads to the remarkable variation of electrical conductivity for the B-, N-, and Si-doped PG, and the adsorption strength of NH3 on the B-, N-, and Si-doped PG is larger than that of H2S and SO2. Moreover, the chemically adsorbed NH3 molecule on the N-, B-, and Si-doped PG can be effectively desorbed by injecting electrons into the systems. Those results shed light on the potential application of PG-based nanosheets as reusable gas sensors for NH3 detection.

Molecules ◽  
2022 ◽  
Vol 27 (2) ◽  
pp. 385
Rachael A. Holt ◽  
Paul G. Seybold

Pyrimidines are key components in the genetic code of living organisms and the pyrimidine scaffold is also found in many bioactive and medicinal compounds. The acidities of these compounds, as represented by their pKas, are of special interest since they determine the species that will prevail under different pH conditions. Here, a quantum chemical quantitative structure–activity relationship (QSAR) approach was employed to estimate these acidities. Density-functional theory calculations at the B3LYP/6-31+G(d,p) level and the SM8 aqueous solvent model were employed, and the energy difference ∆EH2O between the parent compound and its dissociation product was used as a variation parameter. Excellent estimates for both the cation → neutral (pKa1, R2 = 0.965) and neutral → anion (pKa2, R2 = 0.962) dissociations were obtained. A commercial package from Advanced Chemical Design also yielded excellent results for these acidities.

Nanomaterials ◽  
2022 ◽  
Vol 12 (2) ◽  
pp. 199
Kim Eklund ◽  
Antti J. Karttunen

Nitrogen-doped carbon nanotubes (N-CNTs) show promise in several applications related to catalysis and electrochemistry. In particular, N-CNTs with a single nitrogen dopant in the unit cell have been extensively studied computationally, but the structure-property correlations between the relative positions of several nitrogen dopants and the electronic transport properties of N-CNTs have not been systematically investigated with accurate hybrid density functional methods. We use hybrid density functional theory and semiclassical Boltzmann transport theory to systematically investigate the effect of different substitutional nitrogen doping configurations on the electrical conductivity of N-CNTs. Our results indicate significant variation in the electrical conductivity and the relative energies of the different dopant configurations. The findings can be utilized in the optimization of electrical transport properties of N-CNTs.

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