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Articles 1 - 27 of 27
Full-Text Articles in Physical Sciences and Mathematics
Reversible Dioxygen Binding To Co(Ii) Complexes With Noninnocent Ligands, Praveen Kumar, Laxmi Devkota, Maximilian C. Casey, Anne A. Fischer, Sergey V. Lindeman, Adam T. Fiedler
Reversible Dioxygen Binding To Co(Ii) Complexes With Noninnocent Ligands, Praveen Kumar, Laxmi Devkota, Maximilian C. Casey, Anne A. Fischer, Sergey V. Lindeman, Adam T. Fiedler
Chemistry Faculty Research and Publications
A series of mononuclear Co(II) complexes with noninnocent (redox-active) ligands are prepared that exhibit metal–ligand cooperativity during the reversible binding of O2. The complexes have the general formula, [CoII(LS,N)(TpR2)] (R = Me, Ph), where LS,N is a bidentate o-aminothiophenolate and TpR2 is a hydrotris(pyrazol-1-yl)borate scorpionate with R-substituents at the 3- and 5-positions. Exposure to O2 at room temperature results in one-electron oxidation and deprotonation of LS,N. The oxidized derivatives possess substantial “singlet diradical” character arising from antiferromagnetic coupling between an iminothiosemiquinonate (ITSQ•–) …
Saturable Absorption Of Free-Electron Laser Radiation By Graphite Near The Carbon K-Edge, Lars Hoffmann, Sasawat Jamnuch, Craig P. Schwartz, Tobias Helk, Sumana L. Raj, Hikaru Mizuno, Riccardo Mincigrucci, Laura Foglia, Emiliano Principi, Shervin Fatehi
Saturable Absorption Of Free-Electron Laser Radiation By Graphite Near The Carbon K-Edge, Lars Hoffmann, Sasawat Jamnuch, Craig P. Schwartz, Tobias Helk, Sumana L. Raj, Hikaru Mizuno, Riccardo Mincigrucci, Laura Foglia, Emiliano Principi, Shervin Fatehi
Chemistry Faculty Publications and Presentations
The interaction of intense light with matter gives rise to competing nonlinear responses that can dynamically change material properties. Prominent examples are saturable absorption (SA) and two-photon absorption (TPA), which dynamically increase and decrease the transmission of a sample depending on pulse intensity, respectively. The availability of intense soft X-ray pulses from free-electron lasers (FELs) has led to observations of SA and TPA in separate experiments, leaving open questions about the possible interplay between and relative strength of the two phenomena. Here, we systematically study both phenomena in one experiment by exposing graphite films to soft X-ray FEL pulses of …
Band-Gap Tuning In Acceptor-Donor-Acceptor Boron Difluoride Formazanates, Francis L. Buguis, Michael Anghel, Joe B. Gilroy, Jasveer S. Dhindsa
Band-Gap Tuning In Acceptor-Donor-Acceptor Boron Difluoride Formazanates, Francis L. Buguis, Michael Anghel, Joe B. Gilroy, Jasveer S. Dhindsa
Chemistry Publications
π-Conjugated molecules with acceptor-donor-acceptor (A-D-A) electronic structures are an important class of materials due to their tunable optoelectronic properties and applications in, for example, organic light-emitting diodes, nonlinear optical devices, and organic solar cells. The frontier molecular orbital energies, and thus band gaps, of these materials can be tuned by varying the donor and acceptor traits and π-electron counts of the structural components. Herein, we report the synthesis and characterization of a series of A-D-A compounds consisting of BF2 formazanates as electron acceptors bridged by a variety of π-conjugated donors. The results, which are supported by DFT calculations, demonstrate …
Phosphonium Versus Ammonium Compact Polyelectrolyte Complex Networks With Alginate-Comparing Their Properties And Cargo Encapsulation., Tristan D. Harrison, Alexandre J. Salmon, John R. De Bruyn, Paul J. Ragogna, Elizabeth R. Gillies
Phosphonium Versus Ammonium Compact Polyelectrolyte Complex Networks With Alginate-Comparing Their Properties And Cargo Encapsulation., Tristan D. Harrison, Alexandre J. Salmon, John R. De Bruyn, Paul J. Ragogna, Elizabeth R. Gillies
Chemistry Publications
Phosphonium and ammonium polymers can be combined with polyanions to form polyelectrolyte complex (PEC) networks, with potential application in self-healing materials and drug delivery vehicles. While various structures and compositions have been explored, to the best of our knowledge, analogous ammonium and phosphonium networks have not been directly compared to evaluate the effects of phosphorus versus nitrogen cations on the network properties. In this study, we prepared PECs from sodium alginate and poly[triethyl(4-vinylbenzyl)phosphonium chloride], poly[triethyl(4-vinylbenzyl)ammonium chloride], poly[tri(
Brown Carbon Production By Aqueous-Phase Interactions Of Glyoxal And So2, David O. De Haan, Kevin Jansen, Alec D. Rynaski, W. Ryan P. Sueme, Ashley K. Torkelson, Eric T. Czer, Alexander K. Kim, Michael A. Rafla, Audrey C. De Haan, Margaret A. Tolbert
Brown Carbon Production By Aqueous-Phase Interactions Of Glyoxal And So2, David O. De Haan, Kevin Jansen, Alec D. Rynaski, W. Ryan P. Sueme, Ashley K. Torkelson, Eric T. Czer, Alexander K. Kim, Michael A. Rafla, Audrey C. De Haan, Margaret A. Tolbert
Chemistry and Biochemistry: Faculty Scholarship
Oxalic acid and sulfate salts are major components of aerosol particles. Here, we explore the potential for their respective precursor species, glyoxal and SO2, to form atmospheric brown carbon via aqueous-phase reactions in a series of bulk aqueous and flow chamber aerosol experiments. In bulk aqueous solutions, UV- and visible-light-absorbing products are observed at pH 3–4 and 5–6, respectively, with small but detectable yields of hydroxyquinone and polyketone products formed, especially at pH 6. Hydroxymethanesulfonate (HMS), C2, and C3 sulfonates are major products detected by electrospray ionization mass spectrometry (ESI-MS) at pH 5. Past studies …
Measured Optical Absorption Cross Sections Of Tio, Peter Bernath
Measured Optical Absorption Cross Sections Of Tio, Peter Bernath
Chemistry & Biochemistry Faculty Publications
A laboratory emission spectrum of TiO in the visible and near-infrared regions (476–1176 nm) has been calibrated and corrected. High-resolution experimental absorption cross sections for TiO with natural isotopic abundance are provided at a temperature of about 2300 K. These cross sections have been compared with those derived from the ExoMol line list. The experimental cross sections can be used directly as a template for cross correlation TiO detection in hot Jupiter exoplanets.
Investigation Of Solvent Effect On Photophysical Properties Of Some Sulfonamides Derivatives, Ebru Bozkurt, Hali̇se İnci̇ Gül, Mehtap Tuğrak
Investigation Of Solvent Effect On Photophysical Properties Of Some Sulfonamides Derivatives, Ebru Bozkurt, Hali̇se İnci̇ Gül, Mehtap Tuğrak
Turkish Journal of Chemistry
The photophysical properties of new sulfonamides synthesized recently were investigated in different solvents. Shifts in the absorption and fluorescence spectra of both compounds (S10 and S11) occurred depending on the solvents used. Ground and excited state dipole moments of the molecules were calculated using the spectral shifts of the compounds in different solvents and polarity function of solvents, respectively. They were 1.32 and 1.46 D for S10 and 1.71 and 4.89 D for S11. These results suggested that the excited state dipole moments are greater than those in ground state for both molecules. This means that the dyes were more …
Benchmarking Ab Initio Computational Methods For The Quantitative Prediction Of Sunlight-Driven Pollutant Degradation In Aquatic Environments, Kasidet Trerayapiwat
Benchmarking Ab Initio Computational Methods For The Quantitative Prediction Of Sunlight-Driven Pollutant Degradation In Aquatic Environments, Kasidet Trerayapiwat
Honors Projects
Understanding the changes in molecular electronic structure following the absorption of light is a fundamental challenge for the goal of predicting photochemical rates and mechanisms. Proposed here is a systematic benchmarking method to evaluate accuracy of a model to quantitatively predict photo-degradation of small organic molecules in aquatic environments. An overview of underlying com- putational theories relevant to understanding sunlight-driven electronic processes in organic pollutants is presented. To evaluate the optimum size of solvent sphere, molecular Dynamics and Time Dependent Density Functional Theory (MD-TD-DFT) calculations of an aniline molecule in di↵erent numbers of water molecules using CAM-B3LYP functional yielded excited …
Gumbos And Nanogumbos: Applications As Photosensitizers In Dye-Sensitized Solar Cells, Atiya Nicole Jordan
Gumbos And Nanogumbos: Applications As Photosensitizers In Dye-Sensitized Solar Cells, Atiya Nicole Jordan
LSU Doctoral Dissertations
Renewable energy is a major concern due to increased world energy consumption. In particular, solar energy is a type of renewable energy source that uses devices known as solar cells to convert sunlight to electricity. Specifically, devices referred to as dye-sensitized solar cells (DSSCs) employ dyes to absorb solar energy. Dyes derived from ruthenium complexes have been typically used in DSSCs. Unfortunately, several disadvantages are associated with current ruthenium complex photosensitizers, which can be attributed to limited supply and expense of metals, as well as reduced absorption in the near-infrared region of the electromagnetic spectrum. Accordingly, this dissertation is a …
Characterization Of The Desorption Electrospray Ionization Mechanism Using Microscopic Imaging Of The Sample Surface, Michael Craig Wood
Characterization Of The Desorption Electrospray Ionization Mechanism Using Microscopic Imaging Of The Sample Surface, Michael Craig Wood
Theses and Dissertations
Desorption electrospray ionization (DESI) is an ambient ionization technique for mass spectrometry. This solvent based desorption ion source has wide applicability in surface analysis with minimal sample preparation. Interest in improving detection limits, broadening applications, and increasing the spatial resolution for chemical imaging has led to studies of the DESI mechanism. An inverted microscope has been used to image interactions between the DESI spray and test analytes on a glass surface. Microscopic images recorded with millisecond time resolution have provided important insights into the processes governing analyte transport and desorption. These insights are the basis of a rivulet-based model for …
Spectroscopic Properties Of Lanthanide (Iii) Compounds In Aqueous And Ionic Media, Orissa A. Burghard, Sayandev Chatterjee, Zheming Wang, Samuel A. Bryan
Spectroscopic Properties Of Lanthanide (Iii) Compounds In Aqueous And Ionic Media, Orissa A. Burghard, Sayandev Chatterjee, Zheming Wang, Samuel A. Bryan
STAR Program Research Presentations
Lanthanide containing materials are receiving increasing attention due to their wide range of potential applications including bioanalytical imaging, dye-sensitized solar cells, nano-biotechnology and catalysis. The unique spectroscopic properties (intense and sharp emission bands with high color purity and high quantum efficiency) of lanthanides make them strong candidates for use as bio-markers or selective detectors. The attractiveness of lanthanides as future imaging agents as well as recent interest in their potential use in biological media has increased the need to understand the behavior of lanthanides in the presence of other ions or in ionic media.
The complexity of the biological media …
Electronic Properties Of N(5)-Ethyl Flavinium Ion, Vincent Sichula, Pavel Kucheryavy, Renat Khatmullin, Ying Hu, Ekaterina Mirzakulova, Shubham Vyas, Samuel F. Manzer, Christopher M. Hadad, Ksenija D. Glusac
Electronic Properties Of N(5)-Ethyl Flavinium Ion, Vincent Sichula, Pavel Kucheryavy, Renat Khatmullin, Ying Hu, Ekaterina Mirzakulova, Shubham Vyas, Samuel F. Manzer, Christopher M. Hadad, Ksenija D. Glusac
Chemistry Faculty Publications
We investigated the electronic properties of N(5)-ethyl flavinium perchlorate (Et-Fl(+)) and compared them to those of its parent compound, 3-methyllumiflavin (Fl). Absorption and fluorescence spectra of Fl and Et-Fl(+) exhibit similar spectral features, but the absorption energy of Et-Fl(+) is substantially lower than that of Fl. We calculated the absorption signatures of Fl and Et-Fl(+) using time-dependent density functional theory (TD-DFT) methods and found that the main absorption bands of Fl and Et-Fl(+) are (pi,pi*) transitions for the S(1) and S(3) excited states. Furthermore, calculations predict that the S(2) state has (n,pi*) character. Using cyclic voltammetry and a simplistic consideration …
Density Functional Calculation Of X-Ray Absorption Spectra Within The Core Hole Approximation: An Implementation In Nwchem, William Ben Carlen
Density Functional Calculation Of X-Ray Absorption Spectra Within The Core Hole Approximation: An Implementation In Nwchem, William Ben Carlen
Doctoral Dissertations
Density functional theory is used to calculate the core excitation spectra of titanium structures. Specifically, the core-hole approximation is used. In this scenario, the excitation energies of core electrons are calculated using the approximation that the core energy level be frozen throughout the relaxation process of the orbitals. This allows a more acurate determination of the resulting X-ray spectra. The method described has been implemented in an NWChem module.
Ultrafast Optical Study Of Small Gold Monolayer Protected Clusters: A Closer Look At Emission, S. Hei Yau, O. Varnavski, John D. Gilbertson, Bert D. Chandler, G. Ramakrishna, T. Goodson
Ultrafast Optical Study Of Small Gold Monolayer Protected Clusters: A Closer Look At Emission, S. Hei Yau, O. Varnavski, John D. Gilbertson, Bert D. Chandler, G. Ramakrishna, T. Goodson
Chemistry Faculty Research
Monolayer-protected metal nanoclusters (MPCs) were investigated to probe their fundamental excitation and emission properties. In particular, gold MPCs were probed by steady-state and time-resolved spectroscopic measurements; the results were used to examine the mechanism of emission in relation to the excited states in these systems. In steady-state measurements, the photoluminescence of gold clusters in the range of 25 to 140 atoms was considerably stronger relative to larger particle analogues. The increase in emission efficiency (for Au25, Au55, and Au140 on the order of 10-5) over bulk gold may arise from a different mechanism …
Enhanced Absorption Metal Oxides For Photocatalytic Applications, Reenamole Georgekutty
Enhanced Absorption Metal Oxides For Photocatalytic Applications, Reenamole Georgekutty
Doctoral
Environmental pollution and industrialization on a global scale has drawn attention to the vital need for developing new hygienic and environmentally friendly purification technologies. The most common indoor and outdoor purification process have their corresponding limitations of electricity and/or other energy sources. To address such enormous tasks, advance oxidation technology like heterogeneous photocatalytic systems via metal oxide semiconductors such as TiO2, ZnO, that are capable to operate effectively and efficiently under UV and visible light must be established. Due to the wide band gap of semiconductors, they are unable to absorb visible light. Hence, numerous research efforts have been done …
Salt Marshes As A Source Of Chromophoric Dissolved Organic Matter (Cdom) To Southern California Coastal Waters, Catherine D. Clark, Liannea P. Litz, Stanley B. Grant
Salt Marshes As A Source Of Chromophoric Dissolved Organic Matter (Cdom) To Southern California Coastal Waters, Catherine D. Clark, Liannea P. Litz, Stanley B. Grant
Biology, Chemistry, and Environmental Sciences Faculty Articles and Research
To determine chromophoric dissolved organic matter (CDOM) sources in Southern California coastal waters, optical properties of a river outlet and adjacent tidally flushed salt marshes were monitored (dry season; June July 2001). Average absorption coefficients doubled at ebb vs. flood tides (4.8 +/- 1.5 vs. 2.1 +/- 0.9 m(-1); 300 nm), suggesting significant salt marsh CDOM inputs into coastal waters. Average spectral slopes were not statistically different for any sites or tides (0.010 +/- 0.002 nm(-1)), consistent with salt marsh CDOM dominating coastal waters. Three-dimensional fluorescence excitation-emission matrices (EEMs) at ebb tide showed contributions from terrestrial, protein, and marine humic-like …
Yba2cu3o7 Electro-Magneto-Optic Effects In Ba L2,3 X-Ray Absorption Near Tc, Juana Vivó Acrivos
Yba2cu3o7 Electro-Magneto-Optic Effects In Ba L2,3 X-Ray Absorption Near Tc, Juana Vivó Acrivos
Faculty Publications, Chemistry
The onset of electro magneto-optic effects, observed at the Ba L2,3 edges synchrotron X-ray absorption by a YBa2Cu3O7 single crystal, 10 K above the transition temperature to superconductivity, Tc ~ 92 K is used to identify the role played by the Ba donor layer in the transition to superconductivity in the CuO2 layers. Negative permeability leads to Faraday rotation of the transmitted beam below T = 112 to 56 K for the 22 μm thick single crystal (c-axis orientation of 8π/18 relative to εX-rays) and sharp changes in the density of empty final states lead to zero transmitted radiation in …
Yba2cu3o7 Electro-Magneto-Optic Effects In Ba L2,3 X-Ray Absorption Near Tc, Juana Vivó Acrivos
Yba2cu3o7 Electro-Magneto-Optic Effects In Ba L2,3 X-Ray Absorption Near Tc, Juana Vivó Acrivos
Juana Vivó Acrivos
The onset of electro magneto-optic effects, observed at the Ba L2,3 edges synchrotron X-ray absorption by a YBa2Cu3O7 single crystal, 10 K above the transition temperature to superconductivity, Tc ~ 92 K is used to identify the role played by the Ba donor layer in the transition to superconductivity in the CuO2 layers. Negative permeability leads to Faraday rotation of the transmitted beam below T = 112 to 56 K for the 22 μm thick single crystal (c-axis orientation of 8π/18 relative to εX-rays) and sharp changes in the density of empty final states lead to zero transmitted radiation in …
Steady‐State Absorption Rate Models For Use In Relaxation Rate Studies With Continuous Laserexcited Photothermal Lens Spectrometry, Stephen E. Bialkowski
Steady‐State Absorption Rate Models For Use In Relaxation Rate Studies With Continuous Laserexcited Photothermal Lens Spectrometry, Stephen E. Bialkowski
Stephen E. Bialkowski
This paper examines the solutions of kinetic rate equations for prediction of the photothermal lens signals under irradiance conditions that can lead to optical saturation or bleaching. The relaxation kinetics resulting from forcing excited state populations in multiple levels by high excitation irradiance continuous lasers is examined and irradiance-dependent photothermal lens signals are predicted. The analyses described in this paper are based on simple kinetic models for optical excitation and subsequent excited state relaxation. Dark-state relaxation is assumed to be extremely fast compared to limiting kinetics resulting in simplified excited state models. Kinetic models are derived for two, four and …
In-Situ X-Ray-Absorption Spectroscopy Study Of Hydrogen Absorption By Nickel-Magnesium Thin Films, B. Farangis, Ponnusamy Nachimuthu, T. J. Richardson, J. L. Slack, Rupert C. Perera, Eric M. Gullikson, Dennis W. Lindle, M. Rubin
In-Situ X-Ray-Absorption Spectroscopy Study Of Hydrogen Absorption By Nickel-Magnesium Thin Films, B. Farangis, Ponnusamy Nachimuthu, T. J. Richardson, J. L. Slack, Rupert C. Perera, Eric M. Gullikson, Dennis W. Lindle, M. Rubin
Chemistry and Biochemistry Faculty Research
Structural and electronic properties of co-sputtered Ni-Mg thin films with varying Ni to Mg ratio were studied by in-situ x-ray absorption spectroscopy in the Ni L-edge and Mg K-edge regions. Co-deposition of the metals led to increased disorder and decreased coordination around Ni and Mg compared to pure metal films. Exposure of the metallic films to hydrogen resulted in formation of hydrides and increased disorder. The presence of hydrogen as a near neighbor around Mg caused a drastic reduction in the intensities of multiple scattering resonances at higher energies. The optical switching behavior and changes in the x-ray spectra varied …
Conduction Band Symmetry In Ta Chalcogenides From Ta L Edge X-Ray Absorption Spectroscopy (Xas), Juana Vivó Acrivos, S.S. P. Parkin, J. Code, J. Reynolds, K. Hathaway, H. Kurasaki, E. Marseglia
Conduction Band Symmetry In Ta Chalcogenides From Ta L Edge X-Ray Absorption Spectroscopy (Xas), Juana Vivó Acrivos, S.S. P. Parkin, J. Code, J. Reynolds, K. Hathaway, H. Kurasaki, E. Marseglia
Faculty Publications, Chemistry
No abstract provided.
Conduction Band Symmetry In Ta Chalcogenides From Ta L Edge X-Ray Absorption Spectroscopy (Xas), Juana Vivó Acrivos, S.S. P. Parkin, J. Code, J. Reynolds, K. Hathaway, H. Kurasaki, E. Marseglia
Conduction Band Symmetry In Ta Chalcogenides From Ta L Edge X-Ray Absorption Spectroscopy (Xas), Juana Vivó Acrivos, S.S. P. Parkin, J. Code, J. Reynolds, K. Hathaway, H. Kurasaki, E. Marseglia
Juana Vivó Acrivos
No abstract provided.
Analytical Aspects Of Absorption Spectroelectrochemistry At A Platinum Electrode- Ii: Quantitative Basis And Study Of Organic Compounds, Julian Tyson, T. S. West
Analytical Aspects Of Absorption Spectroelectrochemistry At A Platinum Electrode- Ii: Quantitative Basis And Study Of Organic Compounds, Julian Tyson, T. S. West
Chemistry Department Faculty Publication Series
No abstract provided.
Optical Absorption Phenomena At Electrode Surfaces, Julian Tyson, T. S. West
Optical Absorption Phenomena At Electrode Surfaces, Julian Tyson, T. S. West
Chemistry Department Faculty Publication Series
No abstract provided.
Kinetics Of The Decomposition Of The Cupric Ion Sulfhydryl Bond In Beef Plasma Albumin, Gary Rice
Kinetics Of The Decomposition Of The Cupric Ion Sulfhydryl Bond In Beef Plasma Albumin, Gary Rice
Honors Theses
The purpose of this work was to study the kinetics of the binding of cupric ion to beef plasma albumin, in particular the decomposition of the Cu++--BPA complex which absorbs light at 375 millimicrons.
The work of Klotz, Urquhart, Klotz, and Ayers has shown that the characteristic absorption band at 375 mu produced by the binding of cupric ion to beef plasma albumin is due to a copper- sulfhydryl bond. They have further demonstrated that the disappearance of this absorption band with time is accompanied by irreversible changes in the structure of the protein. The intensity of the initial absorption …
Resonance Absorption Of P-Benzosemiquinone In The Zeeman Region, Juana Vivó Acrivos
Resonance Absorption Of P-Benzosemiquinone In The Zeeman Region, Juana Vivó Acrivos
Faculty Publications, Chemistry
No abstract provided.
Resonance Absorption Of P-Benzosemiquinone In The Zeeman Region, Juana Vivó Acrivos
Resonance Absorption Of P-Benzosemiquinone In The Zeeman Region, Juana Vivó Acrivos
Juana Vivó Acrivos
No abstract provided.