From Bioorganic Chemistry to Catalysis

Research projects of the Department of Chemistry, University of Basel are reviewed ranging from the synthesis of complex natural products to the development of metalorganic catalysts and organocatalyst

Full configuration interaction approach to the few-electron problem in artificial atoms

We present a new high-performance configuration interaction code optimally designed for the calculation of the lowest energy eigenstates of a few electrons in semiconductor quantum dots (also called artificial atoms) in the strong interaction regime. The implementation relies on a single-particle representation, but it is independent of the choice of the single-particle basis and, therefore, of the details of the device and configuration of external fields. Assuming no truncation of the Fock space of Slater determinants generated from the chosen single-particle basis, the code may tackle regimes where Coulomb interaction very effectively mixes many determinants. Typical strongly correlated systems lead to very large diagonalization problems; in our implementation, the secular equation is reduced to its minimal rank by exploiting the symmetry of the effective-mass interacting Hamiltonian, including square total spin. The resulting Hamiltonian is diagonalized via parallel implementation of the Lanczos algorithm. The code gives access to both wave functions and energies of first excited states. Excellent code scalability in a parallel environment is demonstrated; accuracy is tested for the case of up to eight electrons confined in a two-dimensional harmonic trap as the density is progressively diluted and correlation becomes dominant. Comparison with previous Quantum Monte Carlo simulations in the Wigner regime demonstrates power and flexibility of the method.Comment: RevTeX 4.0, 18 pages, 6 tables, 9 postscript b/w figures. Final version with new material. Section 6 on the excitation spectrum has been added. Some material has been moved to two appendices, which appear in the EPAPS web depository in the published versio

Excitons, biexcitons, and phonons in ultrathin CdSe/ZnSe quantum structures

The optical properties of CdSe nanostructures grown by migration-enhanced epitaxy of CdSe on ZnSe are studied by time-, energy-, and temperature-dependent photoluminescence and excitation spectroscopy, as well as by polarization-dependent four-wave mixing and two-photon absorption experiments. The nanostructures consist of a coherently strained Zn1−xCdxSe/ZnSe quantum well with embedded islands of higher Cd content with sizes of a few nanometer due to strain-induced CdSe accumulation. The local increase in CdSe concentration results in a strong localization of the excitonic wave function, in an increase in radiative lifetime, and a decrease of the dephasing rate. Local LO-phonon modes caused by the strong modulation of the Cd concentration profile are found in phonon-assisted relaxation processes. Confined biexcitons with large binding energies between 20 and 24 meV are observed, indicating the important role of biexcitons even at room temperature

New Mechanism for Electronic Energy Relaxation in Nanocrystals

The low-frequency vibrational spectrum of an isolated nanometer-scale solid differs dramatically from that of a bulk crystal, causing the decay of a localized electronic state by phonon emission to be inhibited. We show, however, that an electron can also interact with the rigid translational motion of a nanocrystal. The form of the coupling is dictated by the equivalence principle and is independent of the ordinary electron-phonon interaction. We calculate the rate of nonradiative energy relaxation provided by this mechanism and establish its experimental observability.Comment: 4 pages, Submitted to Physical Review

Resonant hyper-Raman scattering in spherical quantum dots

A theoretical model of resonant hyper-Raman scattering by an ensemble of spherical semiconductor quantum dots has been developed. The electronic intermediate states are described as Wannier-Mott excitons in the framework of the envelope function approximation. The optical polar vibrational modes of the nanocrystallites (vibrons) and their interaction with the electronic system are analized with the help of a continuum model satisfying both the mechanical and electrostatic matching conditions at the interface. An explicit expression for the hyper-Raman scattering efficiency is derived, which is valid for incident two-photon energy close to the exciton resonances. The dipole selection rules for optical transitions and Fr\"ohlich-like exciton-lattice interaction are derived: It is shown that only exciton states with total angular momentum $L=0,1$ and vibrational modes with angular momentum $l_p=1$ contribute to the hyper-Raman scattering process. The associated exciton energies, wavefunctions, and vibron frequencies have been obtained for spherical CdSe zincblende-type nanocrystals, and the corresponding hyper-Raman scattering spectrum and resonance profile are calculated. Their dependence on the dot radius and the influence of the size distribution on them are also discussed.Comment: 12 pages REVTeX (two columns), 2 tables, 8 figure

Equilibrium shapes and energies of coherent strained InP islands

The equilibrium shapes and energies of coherent strained InP islands grown on GaP have been investigated with a hybrid approach that has been previously applied to InAs islands on GaAs. This combines calculations of the surface energies by density functional theory and the bulk deformation energies by continuum elasticity theory. The calculated equilibrium shapes for different chemical environments exhibit the {101}, {111}, {\=1\=1\=1} facets and a (001) top surface. They compare quite well with recent atomic-force microscopy data. Thus in the InP/GaInP-system a considerable equilibration of the individual islands with respect to their shapes can be achieved. We discuss the implications of our results for the Ostwald ripening of the coherent InP islands. In addition we compare strain fields in uncapped and capped islands.Comment: 10 pages including 6 figures. Submitted to Phys. Rev. B. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Localization-enhanced biexciton binding in semiconductors

The influence of excitonic localization on the binding energy of biexcitons is investigated for quasi-three-dimensional and quasi-two-dimensional AlxGa1−xAs structures. An increase of the biexciton binding energy is observed for localization energies comparable to or larger than the free biexciton binding energy. A simple analytical model for localization in the weak confinement regime ascribes the increase to a quenching of the additional kinetic energy of the exciton-exciton motion in the biexciton

Broadband semiconductor light sources operating at 1060 nm based on InAs:Sb/GaAs submonolayer quantum dots

In this paper, we investigate the potential of submonolayer-grown InAs:Sb/GaAs quantum dots as active medium for opto-electronic devices emitting in the 1060 nm spectral range. Grown as multiple sheets of InAs in a GaAs matrix, submonolayer quantum dots yield light-emitting devices with large material gain and fast recovery dynamics. Alloying these structures with antimony enhances the carrier localization and red shifts the emission, whereas dramatically broadening the optical bandwidth. In a combined experimental and numerical study, we trace this effect to an Sb-induced bimodal distribution of localized and delocalized exciton states. While the former do not participate in the lasing process, they give rise to a bandwidth broadening at superluminescence operation and optical amplification. Above threshold laser properties like gain and slope efficiency are mainly determined by the delocalized fraction of carriers

Exciton dephasing and biexciton binding in CdSe/ZnSe islands

The dephasing of excitons and the formation of biexcitons in self-organized CdSe/ZnSe islands grown by molecular-beam epitaxy is investigated using spectrally resolved four-wave mixing. A distribution of exciton-exciton scattering efficiencies and dephasing times in the range of 0.5–10 ps are observed. This indicates the presence of differently localized exciton states at comparable transition energies. Polarization-dependent measurements identify the formation of biexcitons with a biexciton binding energy of more than four times the bulk value. With decreasing exciton energy, the binding energy slightly increases from 21.5 to 23 meV, while its broadening decreases from 5.5 to 3 meV. This is attributed to a strong three-dimensional confinement with improving shape uniformity for decreasing exciton energy

Isoelectronic series of oxygen deficient centers in silica: experimental estimation of homogeneous and inhomogeneous spectral widths

We report nanosecond time-resolved photoluminescence measurements on the isoelectronic series of oxygen deficient centers in amorphous silica, Si-ODC(II), Ge-ODC(II) and Sn-ODC(II) which are responsible of fluorescence activities at $\sim$4 eV under excitation at $\sim$5 eV. The dependence of the first moment of their emission band on time, and that of the radiative decay lifetime on emission energy are analyzed within a theoretical model able to describe the effects introduced by disorder on the optical properties of the defects. We obtain separate estimates of the homogeneous and inhomogeneous contributions to the measured emission linewidth and we derive homogeneous spectroscopic features of the investigated point defects (Huangh-Rhys factor, homogeneous width, oscillator strength, vibrational frequency). The results point to a picture in which an oxygen deficient center localized on a heavier atom features a higher degree of inhomogeneity due to stronger local distortion of the surrounding matrix. For Si, Ge, Sn related defects the parameter $\lambda$, able to quantify inhomogeneity, results to be 65, 78 and 90$%, respectively