Quantized evolution of the plasmonic response in a stretched nanorod

Quantum aspects, such as electron tunneling between closely separated metallic nanoparticles, are crucial for understanding the plasmonic response of nanoscale systems. We explore quantum effects on the response of the conductively coupled metallic nanoparticle dimer. This is realized by stretching a nanorod, which leads to the formation of a narrowing atomic contact between the two nanorod ends. Based on first-principles time-dependent density-functional-theory calculations, we find a discontinuous evolution of the plasmonic response as the nanorod is stretched. This is especially pronounced for the intensity of the main charge-transfer plasmon mode. We show the correlation between the observed discontinuities and the discrete nature of the conduction channels supported by the formed atomic-sized junction.Comment: Main text: 6 pages, 2 figures; Supplemental Material: 5 pages, 4 figure

Nanoplasmonics simulations at the basis set limit through completeness-optimized, local numerical basis sets

We present an approach for generating local numerical basis sets of improving accuracy for first-principles nanoplasmonics simulations within time-dependent density functional theory. The method is demonstrated for copper, silver, and gold nanoparticles that are of experimental interest but computationally demanding due to the semi-core d-electrons that affect their plasmonic response. The basis sets are constructed by augmenting numerical atomic orbital basis sets by truncated Gaussian-type orbitals generated by the completeness-optimization scheme, which is applied to the photoabsorption spectra of homoatomic metal atom dimers. We obtain basis sets of improving accuracy up to the complete basis set limit and demonstrate that the performance of the basis sets transfers to simulations of larger nanoparticles and nanoalloys as well as to calculations with various exchange-correlation functionals. This work promotes the use of the local basis set approach of controllable accuracy in first-principles nanoplasmonics simulations and beyond.Comment: 11 pages, 6 figure

Kohn-Sham decomposition in real-time time-dependent density-functional theory: An efficient tool for analyzing plasmonic excitations

The real-time-propagation formulation of time-dependent density-functional theory (RT-TDDFT) is an efficient method for modeling the optical response of molecules and nanoparticles. Compared to the widely adopted linear-response TDDFT approaches based on, e.g., the Casida equations, RT-TDDFT appears, however, lacking efficient analysis methods. This applies in particular to a decomposition of the response in the basis of the underlying single-electron states. In this work, we overcome this limitation by developing an analysis method for obtaining the Kohn-Sham electron-hole decomposition in RT-TDDFT. We demonstrate the equivalence between the developed method and the Casida approach by a benchmark on small benzene derivatives. Then, we use the method for analyzing the plasmonic response of icosahedral silver nanoparticles up to Ag$_{561}$. Based on the analysis, we conclude that in small nanoparticles individual single-electron transitions can split the plasmon into multiple resonances due to strong single-electron-plasmon coupling whereas in larger nanoparticles a distinct plasmon resonance is formed.Comment: 11 pages, 3 figure

Electron transport through quantum wires and point contacts

We have studied quantum wires using the Green's function technique and the density-functional theory, calculating the electronic structure and the conductance. All the numerics are implemented using the finite-element method with a high-order polynomial basis. For short wires, i.e. quantum point contacts, the zero-bias conductance shows, as a function of the gate voltage and at a finite temperature, a plateau at around 0.7G_0. (G_0 = 2e^2/h is the quantum conductance). The behavior, which is caused in our mean-field model by spontaneous spin polarization in the constriction, is reminiscent of the so-called 0.7-anomaly observed in experiments. In our model the temperature and the wire length affect the conductance-gate voltage curves in the same way as in the measured data.Comment: 8 page

Matter-positronium interaction: An exact diagonalization study of the He atom - positronium system

The many-body system comprising a He nucleus, three electrons, and a positron has been studied using the exact diagonalization technique. The purpose has been to clarify to which extent the system can be considered as a distinguishable positronium (Ps) atom interacting with a He atom and, thereby, to pave the way to a practical atomistic modeling of Ps states and annihilation in matter. The maximum value of the distance between the positron and the nucleus is constrained and the Ps atom at different distances from the nucleus is identified from the electron and positron densities, as well as from the electron-positron distance and center-of-mass distributions. The polarization of the Ps atom increases as its distance from the nucleus decreases. A depletion of the He electron density, particularly large at low density values, has been observed. The ortho-Ps pick-off annihilation rate calculated as the overlap of the positron and the free He electron densities has to be corrected for the observed depletion, specially at large pores/voids.Comment: 18 pages, 8 figure

Hydrogen and deuterium decoration of In-vacancy complexes in nickel

The quantum-mechanical states of hydrogen and deuterium in pure and defected nickel have been calculated using the effective-medium theory. The defects considered include monovacancies, the substitutional In impurity, a complex of four vacancies, and a complex of an In impurity decorated with a tetrahedron of four vacancies. While the substitutional In impurity does not trap hydrogen, the vacancy and the vacancy complexes with and without In association do. The calculated binding energy to the four vacancy complex is nearly insensitive to the hydrogen isotopic mass and to the In decoration. These results, along with the dependence of the hydrogen binding energy on multiple hydrogen occupancy of the In vacancy complex, are compared with recent perturbed-angular-correlation experiments.Peer reviewe

Energetics of positron states trapped at vacancies in solids

We report a computational first-principles study of positron trapping at vacancy defects in metals and semiconductors. The main emphasis is on the energetics of the trapping process including the interplay between the positron state and the defect's ionic structure and on the ensuing annihilation characteristics of the trapped state. For vacancies in covalent semiconductors the ion relaxation is a crucial part of the positron trapping process enabling the localization of the positron state. However, positron trapping does not strongly affect the characteristic features of the electronic structure, e.g., the ionization levels change only moderately. Also in the case of metal vacancies the positron-induced ion relaxation has a noticeable effect on the calculated positron lifetime and momentum distribution of annihilating electron-positron pairs.Comment: Submitted to Physical Review B on 17 April 2007. Revised version submitted on 6 July 200