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Results for “density functional calculation”

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At least 1,423 records · Page 79
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Coordination Stoichiometry Effects on the Binding Hierarchy of Histamine and Imidazole–M 2+ Complexes

Histidine–M 2+ coordination bonds are a recognized bond motif in biogenic materials with high hardness and extensibility, which has led to growing interest in their use in soft materials for mechanical function. However, the effect of different metal ions on the stability of the coordination complex remains poorly understood, complicating their implementation in metal-coordinated polymer materials. Herein, rheology experiments and density functional theory calculations are used to characterize the stability of coordination complexes and establish the binding hierarchy of histamine and imidazole with Ni 2+ , Cu 2+ , and Zn 2+ . It is found that the binding hierarchy is driven by the specific affinity of the metal ions to different coordination states, which can be macroscopically tuned by changing the metal-to-ligand stoichiometry of the metal-coordinated network. These findings facilitate the rational selection of metal ions for optimizing the mechanical properties of metal-coordinated materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

First principles density functional theory study of Pb doped α-MnO 2 catalytic materials

Here, the impact of Pb in the tunnels of manganese oxide octahedral molecular sieves on chemical state of Mn species and lattice oxygen were investigated utilizing density functional theory calculations. The results show that the Pb dopant in the tunnels of OMS-2 could reduce the average valence states of Mn. The lower energy required for bulk oxygen defects formation in Pb-OMS-2 validates the activation of lattice oxygen by inclusion of tunnel dopant. The inclusion of Pb promotes the catalytic oxidation activity of OMS-2 by reducing the energy required for the surface lattice oxygen migration during the Mars – van Krevelen oxidation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

An improved model electronic Hamiltonian for potential energy surfaces and spin−orbit couplings of low-lying d−d states of [Fe(bpy){sub 3}]{sup 2+}

With the aim of exploring excited state dynamics, a model electronic Hamiltonian for several low-lying d−d states of [Fe(bpy){sub 3}]{sup 2+} complex [S. Iuchi, J. Chem. Phys. 136, 064519 (2012)] is refined using density-functional theory calculations of singlet, triplet, and quintet states as benchmarks. Spin−orbit coupling elements are also evaluated within the framework of the model Hamiltonian. The accuracy of the developed model Hamiltonian is determined by examining potential energies and spin−orbit couplings at surface crossing regions between different spin states. Insights into the potential energy surfaces around surface crossing regions are also provided through molecular dynamics simulations. The results demonstrate that the constructed model Hamiltonian can be used for studies on the d−d excited state dynamics of [Fe(bpy){sub 3}]{sup 2+}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electronic and topological properties of the van der Waals layered superconductor PtTe

We report the crystal growth and structural and electronic properties of superconducting, van der Waals layered PtTe. Easily cleavable crystals with a platelike morphology consistent with the layered structure were grown from a platinum-rich flux. A consistent determination of T c = 0.57 K is made from the onset of diamagnetism, the zero of resistivity, and the midpoint of the heat-capacity jump. The observed behavior is consistent with type-II superconductivity, with upper critical field at T = 0 estimated using the Werthamer-Helfand-Hohenberg theory to be 143 and 65 Oe for fields out of and in the plane, respectively. The heat-capacity discontinuity is close to the weak-coupling BCS value. Density-functional theory calculations and analysis of the electronic structure finds that PtTe is a topological semimetal with numerous surface states but suggests that the superconducting state itself may be topologically trivial. Additionally, angle-resolved photoemission spectroscopy reveals a normal-state Fermi surface in remarkable agreement with theory and confirms the overall topological nature of the material by experimental identification of the surface bands. Together, these findings identify PtTe as an interesting example of a cleavable, topological, and superconducting material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Quantifying Large Lattice Relaxations in Photovoltaic Devices

Temporal variations of Cu(In,Ga)Se 2 photovoltaic device properties during light exposure at various temperatures and voltage biases for times up to 100 h are analyzed using the kinetic theory of large lattice relaxations. Open-circuit voltage and p-type doping increased with charge injection and decreased with temperature at low injection conditions. Furthermore, lattice relaxation can account for both trends and activation energies extracted from the data are approximately 0.9 and 1.2 eV for devices with lower and higher sodium content, respectively. In these devices, increased sodium content resulted in higher initial p-type doping with greater stability. First-principles calculations providing revised activation energies for the (V Se -V Cu ) complex suggest that this defect does not account for the metastability observed here.

14 SOLAR ENERGY↗
DOE OSTI2015

Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-π{sup 1}*; S{sub 1} state) and the shorter (1π-π{sup 1}*; S{sub 2} state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S{sub 2} state relative to the ground state. Raman excitation profiles of PQ (400–1800 cm{sup −1}) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C{sub 2ν} symmetry constraint on the S{sub 2} state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ti- and Fe-related charge transition levels in $β$ – Ga 2 O 3

Here, deep-level transient spectroscopy measurements on $β$ – Ga 2 O 3 crystals reveal the presence of three defect signatures labeled $E$ 2a , $E$ 2b , and $E$ 3 with activation energies at around 0.66 eV, 0.73 eV, and 0.95 eV below the conduction band edge. Using secondary ion mass spectrometry, a correlation between the defect concentration associated with $E$ 3 and the Ti concentration present in the samples was found. Particularly, it is found that $E$ 3 is the dominant Ti-related defect in $β$ – Ga 2 O 3 and is associated with a single Ti atom. This finding is further corroborated by hybrid functional calculations that predict Ti substituting on an octahedral Ga site, denoted as Ti GaII , to be a good candidate for $E$ 3 . Moreover, the deep level transient spectroscopy results show that the level previously labeled $E$ 2 and attributed to Fe substituting on a gallium site (FeGa) consists of two overlapping signatures labeled E2a and E2b. We tentatively assign $E$ 2a and $E$ 2b to Fe substituting for Ga on a tetrahedral or an octahedral site, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Density functional theory based study of chlorine doped WS{sub 2}-metal interface

Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS{sub 2} with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS{sub 2} supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS{sub 2}.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

High resolution measurements supported by electronic structure calculations of two naphthalene derivatives: [1,5]- and [1,6]-naphthyridine—Estimation of the zero point inertial defect for planar polycyclic aromatic compounds

Polycyclic aromatic hydrocarbons (PAHs) molecules are suspected to be present in the interstellar medium and to participate to the broad and unresolved emissions features, the so-called unidentified infrared bands. In the laboratory, very few studies report the rotationally resolved structure of such important class of molecules. In the present work, both experimental and theoretical approaches provide the first accurate determination of the rotational energy levels of two diazanaphthalene: [1,5]- and [1,6]-naphthyridine. [1,6]-naphthyridine has been studied at high resolution, in the microwave (MW) region using a Fourier transform microwave spectrometer and in the far-infrared (FIR) region using synchrotron-based Fourier transform spectroscopy. The very accurate set of ground state (GS) constants deduced from the analysis of the MW spectrum allowed the analysis of the most intense modes in the FIR (ν{sub 38}-GS centered at about 483 cm{sup −1} and ν{sub 34}-GS centered at about 842 cm{sup −1}). In contrast with [1,6]-naphthyridine, pure rotation spectroscopy of [1,5]-naphthyridine cannot be performed for symmetry reasons so the combined study of the two intense FIR modes (ν{sub 22}-GS centered at about 166 cm{sup −1} and ν{sub 18}-GS centered at about 818 cm{sup −1}) provided the GS and the excited states constants. Although the analysis of the very dense rotational patterns for such large molecules remains very challenging, relatively accurate anharmonic density functional theory calculations appeared as a highly relevant supporting tool to the analysis for both molecules. In addition, the good agreement between the experimental and calculated infrared spectrum shows that the present theoretical approach should provide useful data for the astrophysical models. Moreover, inertial defects calculated in the GS (Δ{sub GS}) of both molecules exhibit slightly negative values as previously observed for planar species of this molecular family. We adjusted the semi-empirical relations to estimate the zero-point inertial defect (Δ{sub 0}) of polycyclic aromatic molecules and confirmed the contribution of low frequency out-of-plane vibrational modes to the GS inertial defects of PAHs, which is indeed a key parameter to validate the analysis of such large molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The Coordination Behaviour of Cu I Photosensitizers Bearing Multidentate Ligands Investigated by X-ray Absorption Spectroscopy

A systematic series of four novel homo- and heteroleptic CuI photosensitizers based on tetradentate 1,10-phenanthroline ligands of the type X^N^N^X containing two additional donor moieties in the 2,9-position (X=SMe or OMe) were designed. Their solid-state structures were assessed by X-ray diffraction. Cyclic voltammetry, UV-vis absorption, emission and X-ray absorption spectroscopy were then used to determine their electrochemical, photophysical and structural features in solution. Following, time-resolved X-ray absorption spectroscopy in the picosecond time scale, coupled with time-dependent density functional theory calculations, provided in-depth information on the excited state electron configurations. For the first time, a significant shortening of the Cu–X distance and a change in the coordination mode to a pentacoordinated geometry is shown in the excited states of the two homoleptic complexes. These findings are important with respect to a precise understanding of the excited state structures and a further stabilization of this type of photosensitizers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effects of cation concentration on photocatalytic performance over magnesium vanadates

A series of magnesium vanadates (MgV {sub 2}O{sub 6}, Mg{sub 2}V {sub 2}O{sub 7}, and Mg{sub 3}V {sub 2}O{sub 8}) were synthesized to investigate the effect of cation concentration on photocatalytic performance. The samples were characterized by X-ray diffraction, field emission-scanning electron microscopy, UV-visible diffuse reflectance spectroscopy, and fluorescence spectroscopy. The photocatalytic O{sub 2} evolution experiments under visible light irradiation showed Mg{sub 2}V {sub 2}O{sub 7} exhibits the best performance, while Mg{sub 3}V {sub 2}O{sub 8} has the lowest activity. The density functional theory calculations indicated that the lowest unoccupied states of Mg{sub 3}V {sub 2}O{sub 8} are the mostly localized by the cation layers. The fluorescence spectra and fluorescence decay curves gave evident performances of excited states of magnesium vanadates and pointed out MgV {sub 2}O{sub 6} has a very short excited electron lift-time. Mg{sub 2}V {sub 2}O{sub 7} performs high photocatalytic activity because of its high electron mobility and long electron life-time.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Synthesis of photochromic nanoparticles and determination of the mechanism of photochromism

Photochromic nanoparticles of zinc-silicon oxide were synthesized using plasma enhanced chemical vapor deposition. These particles turned black upon irradiating with ultraviolet light. We investigated this phenomenon using density functional theory calculations. Silicon inclusions create trap levels and oxygen defects that reduce the ionization potential of ZnO. This forms a quantum potential between ZnO and zinc-silicon oxide, and the excited electron is stable. Because oxygen defects also increase the bond overlap population between the zinc atoms in a ZnO crystal, they introduce further defects and help in the formation of quantum potentials. Growth of a perfect crystal of ZnO prevents the formation of oxygen defects, which is not desirable for photochromism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Vibrational Entropy Contribution to Mixing Free Energy of Ni-Rich LiNi 1- y Co y O 2

First principles density-functional-theory calculations are performed of the mixing free energy of the layered oxide LiNi 1-y Co y O 2 , a model Li-ion-battery cathode material, at 1000 K. Analysis of internal energy, LN exchange, configurational entropy and vibrational entropy are combined to obtain the net mixing free energy. The vibrational entropy requires a more indirect treatment than the other terms; analysis based on heat capacity is presented here, to show that the vibrational entropy is of comparable magnitude to the configurational entropy, and it tends to promote solid-solution behavior in LiNi 1-y Co y O 2 .

25 ENERGY STORAGE↗
DOE OSTI2019

Colloidal silver diphosphide (AgP 2 ) nanocrystals as low overpotential catalysts for CO 2 reduction to tunable syngas

Production of syngas with tunable CO/H 2 ratio from renewable resources is an ideal way to provide a carbon-neutral feedstock for liquid fuel production. Ag is a benchmark electrocatalysts for CO 2 -to-CO conversion but high overpotential limits the efficiency. We synthesize AgP 2 nanocrystals (NCs) with a greater than 3-fold reduction in overpotential for electrochemical CO 2 -to-CO reduction compared to Ag and greatly enhanced stability. Density functional theory calculations reveal a significant energy barrier decrease in the formate intermediate formation step. In situ X-ray absorption spectroscopy (XAS) shows that a maximum Faradaic efficiency is achieved at an average silver valence state of +1.08 in AgP 2 NCs. A photocathode consisting of a n + p-Si wafer coated with ultrathin Al 2 O 3 and AgP 2 NCs achieves an onset potential of 0.2 V vs. RHE for CO production and a partial photocurrent density for CO at –0.11 V vs. RHE ( j –0.11, CO ) of –3.2 mA cm –2 .

Heterogeneous catalysis↗
DOE OSTI2022

A metal-supported single-atom catalytic site enables carbon dioxide hydrogenation

Nitrogen-doped graphene-supported single atoms convert CO 2 to CO, but fail to provide further hydrogenation to methane – a finding attributable to the weak adsorption of CO intermediates. To regulate the adsorption energy, here we investigate the metal-supported single atoms to enable CO 2 hydrogenation. We find a copper-supported iron-single-atom catalyst producing a high-rate methane. Density functional theory calculations and in-situ Raman spectroscopy show that the iron atoms attract surrounding intermediates and carry out hydrogenation to generate methane. The catalyst is realized by assembling iron phthalocyanine on the copper surface, followed by in-situ formation of single iron atoms during electrocatalysis, identified using operando X-ray absorption spectroscopy. The copper-supported iron-single-atom catalyst exhibits a CO 2 -to-methane Faradaic efficiency of 64% and a partial current density of 128 mA cm –2 , while the nitrogen-doped graphene-supported one produces only CO. The activity is 32 times higher than a pristine copper under the same conditions of electrolyte and bias.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Preferential Location of Germanium in the UTL and IPC-2a Zeolites

The preferential location of Ge in the double four-membered (D 4 R) rings of UTL has been examined with periodic density functional theory calculations. In silicate UTL, Ge atoms are preferentially sited at T1 and T2, the atoms in the D 4 R cages. Overall, the preference for siting Ge atoms in UTL depends strongly on the average T-O T angles centered at each site. The sites in the D 4 R cages have the lowest average T-O-T angles. Also, the preference for siting Ge atoms at the D 4 R sites in UTL increases as more Si atoms are replaced by Ge. Our calculations show that at least 3 Ge atoms can be located in the D 4 R cages before any appreciable occupancy at non-D 4 R sites. As a result, comparison of Ge atom siting in UTL to IPC-2a shows that the single four-membered ring (S 4 R) sites in the latter are not the most favorable sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The striking influence of oxophilicity differences in heterometallic Mo–Mn oxide cluster reactions with water

Mixed-metal oxides have proven to be effective catalysts for the hydrogen evolution reaction, often outperforming either of the binary metal oxides. The reactivity of Mn x MoO y - (x = 1, 2; y = 3, 4) clusters toward H 2 O was investigated via time-of-flight mass spectrometry with clear evidence of cluster oxidation and corresponding H 2 production, specifically for Mn x MoO 3 - (x = 1, 2) clusters. Unlike previously studied MoxOy- clusters, which assumed a broad distribution of stoichiometries (typically x ≤ y ≤ 3x), both MnMoOy- and Mn 2 MoO y - preferentially formed y = 3 and 4 compositions in significant quantities under our source conditions. The electronic and molecular structures of the Mn x MoO y (x = 1, 2; y = 3, 4) anion and neutral clusters were probed with anion photoelectron spectroscopy and analyzed with supporting density functional theory calculations. Our studies suggest that both metal centers are involved in initial cluster–water complex formation, while Mo is the center that undergoes oxidation; hence, reactivity terminates when Mo is saturated in its highest oxidation state of +6. Across these four clusters, Mn remains relatively reduced and is stable in a high-spin electronic configuration. The preferential reactivity of water molecules toward the Mo center rather than Mn is rationalized by the much lower relative oxophilicity of Mn.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Chemical control of the Rashba spin splitting size of α-GeTe(111) surface states by adjusting the potential at the topmost atomic layer

As control of the Rashba spin splitting size is highly desirable for spintronic devices, intensive studies have been performed to vary the splitting size by, for example, applying an electric field or designing novel heterostructures. However, direct observation of Rashba spin splitting size change via spectroscopic measurements has not been done so far. Here, we report results of angle-resolved photoemission studies on ferroelectric α-GeTe(111). We observe that the Rashba splitting size of α-GeTe(111) surface states is reduced upon dosing with potassium (K) which has a very low electron affinity. Based on density functional theory calculations, we find that the electric potential energy at the topmost atomic layer and the surface potential energy barrier is reduced upon K dosing. Furthermore, this change in the surface potential induces both delocalization of the surface states and reduction of the splitting size. We expect to increase the splitting size by dosing other elements or molecules with high electron affinity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗