Quantum mechanical calculation of the optical absorption of silver and gold nanoparticles by density functional theory

Problem statement: Metal nanoparticles confine the motion of conduction electrons and exhibit a strong optical absorption of electromagnetic radiation in the UV-vis-NIR region. The absorption is classically derived from the collective oscillations of free electrons in a metallic nanostructure as a consequence of incident electromagnetic radiation polarizing the particle optically embedded in a dielectric matrix. These oscillations, known as the localized surface Plasmon resonance has been modelled by Gustav Mie in 1908 using the Maxwell's equations. Nevertheless, the electrodynamics approach cannot account for the electronic transitions often displayed in experiment as a broad UV-vis optical absorption spectrum originated from the conduction electrons of metal nanoparticles. A quantum mechanical approach is required to address the optical absorption spectra of metal nanoparticles systemically. Approach: In this study, an attempt was made to calculate the optical absorption spectra of conduction electrons of metal nanoparticle quantum mechanically using the density functional theory. The particle was an isolated spherical metal nanoparticle containing N atoms confined in a face-centered cubic lattice structure. When light strikes the particle, the occupied ground-state conduction electrons absorbed the energy and excite to the unoccupied higher energy-state of the conduction band. In this development, we used time-independent Schrodinger equation for the ground-state energy of Thomas-Fermi-Dirac-Weizsacker atomic model for the total energy functional and the density function in the Euler-Lagrange equation is algebraically substituted with the absorption function. The total energy functional was computed numerically for silver and gold nanoparticles at various diameters. Results: The results showed broad absorption spectra derived from the occupied ground-state conduction electrons at the orbital {n = 5 and l = 0 or 5s} for silver and {n = 6 and l = 0 or 6s} for gold, which excite to the unoccupied higher energy of conduction band at the orbital {n≥6 and l = 0 or 1} for silver and {n≥7 and l = 0 or 1} for gold. A nonlinear red-shift of the absorption peak λmax, appearing at 404.79, 408.36, 412.55, 415.73, 418.42 and 420.96 nm for silver and at 510.28, 520.91, 533.11, 542.35, 549.74 and 556.04 nm for gold when the particle diameter varies at 4, 5, 7, 10, 15 and 25 nm respectively. The quantum confinement effect of the conduction bands is stronger for silver and gold nanoparticles of less than about 20 nm in diameter. Conclusion: The optical absorption spectra of silver and gold nanoparticles have been successfully calculated using a quantum treatment and this calculation could be extended to other transition metal nanoparticles of interest in nanoscience and nanotechnology

Band gap of cubic and hexagonal CdS quantum dots - experimental and theoretical studies

CdS quantum dots of face centered cubic (fcc) and hexagonal close packed (hcp) structures were synthesized from sulphur source of sodium sulphide and thioacetamide respectively via microwave-hydrothermal method. The synthesized quantum dots were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-visible spectrophotometry. The average particle size in the range 8.5 - 12.5 nm increases with the increase of microwave exposure time from 10 to 40 min. Particles with hcp structure are larger than those with the fcc structure. The band gap in the range 2.54 - 2.65 eV decreases with the increase of microwave exposure time and the particles with the hcp structure have larger band gap than those with the fcc structure. The band gap of the CdS quantum dots were also derived from time independent Schrodinger equations for CdS system and calculated using the density functional theory (DFT). There is good agreement between the measured and calculated band gap values. The results also reveal that the band gap decreases with the increase of particle size due to the quantum size effects

Distribution of trace elements in core marine sediments of coastal East Malaysia by instrumental neutron activation analysis

A study was carried out on the distribution and enrichment of trace elements in the core marine sediments of East Malaysia from three stations at South China Sea and one station each at Sulu Sea and Sulawesi Sea. Five stations of sediment cores were recovered and the vertical concentration profiles of six elements namely Br, Cs, Hf, Rb, Ta, and V were determined using the instrumental neutron activation analysis. The enrichment factor, geoaccumulation index and the modified degree of contamination were used to calculate the anthropogenic and pollution status of the elements in the samples. Except for Cs and Hf, which by the enrichment factor are categorized from minimum enrichment to moderate enrichment in all stations and for V and Rb in Sulu Sea and Sulawesi Sea, which are categorized minimum enrichment, other elements are found to be no enrichment at all stations. The geoaccumulation index of Hf in one station shows moderately polluted and for other elements are unpolluted. However, the modified degree values of all samples are less than 1, suggesting very low contamination of elements found in all the stations

Distribution of heavy metals in core marine sediments of coastal East Malaysia by instrumental neutron activation analysis and inductively coupled plasma spectroscopy

Fifty-five core marine sediments from three locations at South China Sea and one location each at Sulu Sea and Sulawesi Sea of coastal East Malaysia were analyzed for heavy metals by instrumental neutron activation analysis and inductively coupled plasma mass spectroscopy. The enrichment factor and the modified degree of contamination were used to calculate the anthropogenic and pollution status of the elements in the samples. The enrichment factor of As, Cd, Cr, Cu, Ni, Pb, and Zn varied from 0.42-4.26, 0.50–2.34, 0.31–0.82, 0.20–0.61, 0.91–1.92, 0.23–1.52, and 0.90–1.28, respectively, with the modified degree of contamination values below 0.6. Comparative data showed that coastal East Malaysia has low levels of contamination

Photocatalytic degradation of methylene blue under visible light using PVP-capped ZnS and CdS nanoparticles

Photocatalysis based on semiconductor quantum dots which utilize the solar energy can be used for the elimination of pollutants from aqueous media and applied for water purification. Degradation of dyes is a standard method to check the photocatalytic activity of any type of photocatalyst. In this paper polyvinyl pyrrolidone (PVP)-capped ZnS and CdS nanoparticles were prepared by a simple microwave irradiation method and studied in detail for their photocatalytic activity in visible range. The obtained nanoparticles were characterized by XRD, TEM, UV–Vis and EDX. The prepared PVP-capped ZnS and CdS nanoparticles have average sizes of ∼5.1 and 18.3 nm with cubic and hexagonal crystalline structures, respectively. PVP capped CdS nanoparticles exhibited a unique property of optical absorption in visible region with a wave length below than 460 nm followed by a clear long tail up to 700 nm and showed excellent activity toward degradation of dye under visible light illumination. The photocatalytic activity of PVP-capped CdS nanoparticles was found to be improved by mixing with appropriate amount of PVP-capped ZnS nanoprticles. From the study of variation in weight percentages of PVP-capped ZnS nanoparticles, the physical mixture with 20% of PVP-capped ZnS nanoparticles was found to be very efficient for degradation of methylene blue. In this case the degradation efficiency after 6 h illumination was about 81%

Structural, optical and electrical properties of ZnS nanoparticles affecting by organic coating

In this study the influence of the organic polymeric coating and its concentration on the structural, optical and electrical properties of ZnS nanocrystals has been investigated. In this matter, PVP-capped ZnS nanocrystals were prepared by a simple, rapid and energy efficient microwave method. The XRD results confirmed the formation of single phase cubic nano crystalline structure. TEM images showed the formation of well isolated spherical nanoparticles with the average size of less than 5.5 nm. The presence of tensile strain in all samples was determined from Williamson-Hall analysis. The elemental compositions of Zn, S and O were quantitatively obtained from EDX analysis, where the FT-IR spectra confirmed coordination with O atoms of PVP. The band gap and absorption edge shift was determined using UV–visible spectroscopy. The PL spectra of the PVP-capped ZnS nanoparticles appeared broadened from 370 to 500 nm due to the presence of multiple emission bands attribute to the sulfur and zinc vacancies or compounded effect of PVP. The electrical property study of samples indicated the conductivity enhancement from 2.981×10-6 to 7.014 ×10-6 S/m by increasing PVP concentration. Increasing of dielectric constant and decrease in the peak value of tan δ by raising the PVP concentration were observed

Up-scalable synthesis of size-controlled copper ferrite nanocrystals by thermal treatment method

Close-packed cubic copper ferrites (CuFe2O4) nanoparticles were synthesized using an effective thermal-treatment method directly from an aqueous solution containing copper and iron nitrates as metal precursors and poly(vinyl pyrrolidone) as a capping agent. The FTIR spectra of the calcined samples revealed the vibration bands of Fe–O and Cu–O at 315 and 535 nm respectively. The structural, morphological, optical and magnetic properties of the nanocrystal powder samples were analyzed using various characterization techniques. The powder X-ray diffraction unveiled the formation of spinel phase of CuFe2O4 with the average particle size determined from TEM images increased from 24 to 34 nm at the calcination temperatures between 773 and 1173 K. The band gap calculated using Kubelka–Munk function from the UV–visible diffuse reflectance spectra decreased from 2.64 to 2.45 eV with increasing calcination temperature. The electron spin resonance (ESR) spectroscopy confirmed the presence of unpaired electrons in the calcined samples. The g-factor increased from 2.10497 to 2.57056 and the resonance magnetic field decreased from 3.11599×10−7 to 2.55161×10−7 A/m with increasing calcination temperature

Numerical study of side gate junction-less transistor in on state

Side gate p-type Junctionless Silicon transistor is fabricated by AFM nanolithography on low-doped (105 cm-3) SOI wafer. In this work, the simulation characteristic of the device using TCAD Sentaurus in on state will be studied. The results show that the device is the pinch off transistor, works in on state for zero gate voltage in depletion mode. Negative gate voltage drives the device into on state, but unable to make significant effect on drain current as accmulation mode. Simulation results for valence band energy, electric field and hole density are investigated along the active regions. The influence of the electric field due to the applied voltages of V DS and V G on charge distribution is much more when the device operates at the saturation region. The hole quasi-Fermi level has a positive slope showing the current flows from source to drain

Synthesis and characterization of Zeolite/Fe3O4 nanocomposite by green quick precipitation method.

A green quick precipitation method was successfully used for synthesis of magnetic iron oxide nanoparticles (Fe3O4-NPs) on the surface of sodium/potassium type zeolite. Ferric chloride, ferrous chloride and sodium hydroxide aqueous solutions were used in the synthesis and coating of the Fe3O4-NPs on the surface of the zeolite to produce the zeolite/magnetic iron oxide nanocomposite (zeolite/Fe3O4 –NCs). The reaction was performed in aqueous suspension phase under the ambient condition as green chemistry method. Characterization with Fourier transforms infrared spectroscopy (FT‒IR), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive X-ray fluorescence (EDXF) and transmission electron microscopy (TEM) confirmed the formation of Fe3O4-NPs with mean particle sizes of 3.55±1.02 nm on the surface of the zeolite