441 research outputs found
Oscillator strengths with pseudopotentials
The time-dependent local-density approximation (TDLDA) is shown to remain
accurate in describing the atomic response of IB elements under the additional
approximation of using pseudopotentials to treat the effects of core electrons.
This extends the work of Zangwill and Soven who showed the utility of the
all-electron TDLDA in the atomic response problem.Comment: 13 pages including 3 Postscript figure
Hypothalamic Neuroendocrine Functions in Rats with Dihydrotestosterone-Induced Polycystic Ovary Syndrome: Effects of Low-Frequency Electro-Acupuncture
Adult female rats continuously exposed to androgens from prepuberty have reproductive and metabolic features of polycystic ovary syndrome (PCOS). We investigated whether such exposure adversely affects estrous cyclicity and the expression and distribution of gonadotropin-releasing hormone (GnRH), GnRH receptors, and corticotrophin-releasing hormone (CRH) in the hypothalamus and whether the effects are mediated by the androgen receptor (AR). We also assessed the effect of low-frequency electro-acupuncture (EA) on those variables. At 21 days of age, rats were randomly divided into three groups (control, PCOS, and PCOS EA; n = 12/group) and implanted subcutaneously with 90-day continuous-release pellets containing vehicle or 5α-dihydrostestosterone (DHT). From age 70 days, PCOS EA rats received 2-Hz EA (evoking muscle twitches) five times/week for 4–5 weeks. Hypothalamic protein expression was measured by immunohistochemistry and western blot. DHT-treated rats were acyclic, but controls had regular estrous cycles. In PCOS rats, hypothalamic medial preoptic AR protein expression and the number of AR- and GnRH-immunoreactive cells were increased, but CRH was not affected; however, GnRH receptor expression was decreased in both the pituitary and hypothalamus. Low-frequency EA restored estrous cyclicity within 1 week and reduced the elevated hypothalamic GnRH and AR expression levels. EA did not affect GnRH receptor or CRH expression. Interestingly, nuclear AR co-localized with GnRH in the hypothalamus. Thus, rats with DHT-induced PCOS have disrupted estrous cyclicity and an increased number of hypothalamic cells expressing GnRH, most likely mediated by AR activation. Repeated low-frequency EA normalized estrous cyclicity and restored GnRH and AR protein expression. These results may help explain the beneficial neuroendocrine effects of low-frequency EA in women with PCOS
AgPd, AuPd, and AuPt nanoalloys with Ag- or Au-rich compositions: Modeling chemical ordering and optical properties
Bimetallic nanoparticles have a myriad of technological applications, but investigations of their chemical and physical properties are precluded due to their structural complexity. Here, the chemical ordering and optical properties of AgPd, AuPd, and AuPt nanoparticles have been studied computationally. One of the main aims was to clarify whether layered ordered phases similar to L11 one observed in the core of AgPt nanoparticles [Pirart, J.; Nat. Commun. 2019, 10, 1982] are also stabilized in other nanoalloys of coinage metals with platinum-group metals, or the remarkable ordering is a peculiarity only of AgPt nanoparticles. Furthermore, the effects of different chemical orderings and compositions of the nanoalloys on their optical properties have been explored. Particles with a truncated octahedral geometry containing 201 and 405 atoms have been modeled. For each particle, the studied stoichiometries of the Ag- or Au-rich compositions, ca. 4:1 for 201-atomic particles and ca. 3:1 for 405-atomic particles, corresponded to the layered structures L11 and L10 inside the monatomic coinage-metal skins. Density functional theory (DFT) calculations combined with a recently developed topological (TOP) approach [Kozlov, S. M.; Chem. Sci. 2015, 6, 3868−3880] have been performed to study the chemical ordering of the particles, whose optical properties have been investigated using the time-dependent DFT method. The obtained results revealed that the remarkable ordering L11 of inner atoms can be noticeably favored only in small AgPt particles and much less in AgPd ones, whereas this L11 ordering in analogous Au-containing nanoalloys is significantly less stable compared to other calculated lowest-energy orderings. Optical properties were found to be more dependent on the composition (concentration of two metals) than on the chemical ordering. Both Pt and Pd elements promote the quenching of the plasmon
Optical properties and chemical ordering of Ag-Pt nanoalloys: a computational study
A series of core@shell and layered ordered phases of AgPt bimetallic nanoparticles has been studied with Ag:Pt = 3:1 and 6:1 atomic compositions and sizes from 116 to 201 atoms. The elementary chemical order has been established by using a recent method (TOP), which assigns energy according to different topological degrees of freedom. The TOP lowest-energy structures, confirmed by density functional calculations, are then studied by time dependent density functional theory in order to calculate optical properties. The present study shows that for AgPt nanoparticles with core@shell structure the optical properties are sensitive to both the Pt concentration and system size. Spectral trends related to chemical order have also been identified
On the photoionization of the outer electrons in noble gas endohedral atoms
We demonstrate the prominent modification of the outer shell photoionization
cross-section in noble gas (NG) endohedral atoms NG@F under the action of the
fullerene F electron shell. This shell leads to two important effects, namely
to strong enhancement of the cross-section due to fullerenes shell polarization
under the action of the incoming electromagnetic wave and to prominent
oscillation of this cross-section due to the reflection of the photoelectron
from NG by the F shell.
All but He noble gas atoms are considered. The polarization of the fullerene
shell is expressed via the total photoabsorption cross-section of F. The
reflection of the photoelectron is taken into account in the frame of the
so-called bubble potential that is a spherical zero --thickness potential.
It is assumed in the derivations that NG is centrally located in the
fullerene. It is assumed also, in accord with the existing experimental data,
that the fullerenes radius R is much bigger than the atomic radius and the
thickness of the fullerenes shell . These assumptions permit, as it was
demonstrated recently, to present the NG@F photoionization cross-section as a
product of the NG cross-section and two well defined calculated factors.Comment: 19 pages, 9 figure
Diffraction effects in the Recoil-Frame Photoelectron Angular Distributions of Halomethanes
Citation: Bomme, C., Anielski, D., Savelyev, E., Boll, R., Erk, B., Bari, S., . . . Rolles, D. (2015). Diffraction effects in the Recoil-Frame Photoelectron Angular Distributions of Halomethanes. 635(11). doi:10.1088/1742-6596/635/11/112020We have measured the Recoil Frame-Photoelectron Angular Distributions (RF-PADs) for inner-shell photoionization of CH3F, CH3I and CF3I halomethane molecules for photoelectron energies up to 300 eV detected within a 4? solid angle in the gas-phase. For high kinetic energies, the RF-PADs are dominated by diffraction effects that encode information on the molecular geometry. © Published under licence by IOP Publishing Ltd
Probing Intermolecular H-Bonding Interactions in Cyanuric Acid Networks: Quenching of the N K-Edge Sigma Resonances
The electronic characterization of the cyanuric acid both in gas phase and when embedded within an H-bonded scheme forming a monolayer on the Au(111) surface has been performed by means of X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The experimental spectra at the N, O, and C K-edges have been assigned with the support of DFT calculations, and the combination between theory and experiment has allowed to us investigate the effect of the H-bonding intermolecular interaction on the spectra. In particular, the H-bond formation in the monolayer leads to a quenching of the N 1s NEXAFS resonances associated with transitions to the sigma empty orbitals localized on the N-H portion of the imide group. On the other hand, the pi* empty states remain substantially unperturbed. From a computational point of view, it has been shown that the DFT-TP scheme is not able to describe the N 1s NEXAFS spectra of these systems, and the configuration mixing has to be included, through the TDDFT approach in conjunction with the range-separated XC CAM-B3LYP functional, to obtain a correct reproduction of the N 1s core spectra
Application of time-dependent density functional theory to optical activity
As part of a general study of the time-dependent local density approximation
(TDLDA), we here report calculations of optical activity of chiral molecules.
The theory automatically satisfies sum rules and the Kramers-Kronig relation
between circular dichroism and optical rotatory power. We find that the theory
describes the measured circular dichroism of the lowest states in methyloxirane
with an accuracy of about a factor of two. In the chiral fullerene C_76 the
TDLDA provides a consistent description of the optical absorption spectrum, the
circular dichroism spectrum, and the optical rotatory power, except for an
overall shift of the theoretical spectrum.Comment: 17 pages and 13 PostScript figure
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