Ultrafast relaxation dynamics of electronic excitations in noble-metal clusters

We investigate non-equilibrium relaxation processes in optically excited large gold and silver clusters. Time-resolved pump-probe experiments and model calculations show that optical excitation of the clusters by femtosecond laser pulses results in a heating of the electron system, which is followed by electron cooling via phonon emission. The electron heating leads to an enhanced damping of the surface-plasmon resonance in the clusters. This enhanced damping is caused by an enhancement of the Landau damping and electron scattering rates at high electron temperatures. Furthermore, we find that the rate of electron cooling in the clusters changes with electron temperature; this is a consequence of the temperature-dependent specific heat of the conduction electrons. Finally, pump-probe experiments on ellipsoidal silver clusters show that the thermal expansion of the heated clusters triggers mechanical vibrations at the acoustic eigenfrequencies of the clusters. Received: 6 December 1999 / Published online: 7 August 2000     

Collective electronic excitations in clusters in the vicinity of metal surfaces

We study the collective excitations of metal clusters approaching a metal surface. Using a simple model for the frequency-dependent dielectric constant ε(ω) and the multiple scattering method, we numerically investigate the shift in the plasmon resonance due to the coupling of the collective modes of the sphere with those of its mirror image. Results of the model calculation are verified by means of ab initio theory. As a prototype system we study Na₉ ⁺ cluster on the Cu(100) surface. The representation of the solid surface by a cluster of several, typically 54 substrate atoms, is used in combination with a high level configuration interaction (CI) calculation. PACS 31.15.Dv; 36.40.Gk; 73.20.-f     

Influence of electronic excitations on the thermodynamics of small carbon clusters: the example of C3 +

We illustrate the influence of the thermalization of electrons on the linear-cyclic isomerization of small carbon clusters by model Monte Carlo calculations of C₃ ⁺ at 3500 K. It is shown that the inclusion of the electronic degrees of freedom, in such systems with several low-lying excited states, can significantly change the relative isomer populations and energy distributions, as compared with equivalent electronic ground-state simulations.     

Direct STM observation of electronic structure modification of naphthacenequinone molecules due to photoisomerization

Light-induced conformational transformations of the naphthacenequinone (NQ) molecules are observed by scanning tunneling microscopy (STM). NQ molecules packed in a Langmuir-Blodgett (LB) film are shown to form stable ordered structures on a surface of highly oriented pyrolytic graphite (HOPG). The local density of electronic states is found to exhibit the distinct peak which is characteristic of two-dimensional conductivity. An additional subband of empty electronic states is found for NQ molecules in form A but not in form B. The constant-height STM images of individual molecules in form A demonstrate an additional structure that is indicative of a conformational transition of the NQ molecules. This transition involves the transfer of the phenoxy group from one oxygen to another. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 6, 486–490 (25 September 1998)     

Collectivity of plasmon excitations in small sodium clusters with planar structure

The collectivity of the electronic motion in small sodium clusters with planar structure is studied by the time-dependent density functional theory (TDDFT). The formation and development of collective resonances in the absorption spectra were obtained as the function of the size and shape of the plane. We find the symmetry plays an important role in the collective excitation. Resonance peaks increase with the reduction of the symmetries and, on the contrary, resonance peaks decrease with the increase of the symmetries. In the planar cluster, there are two main excitation modes: the higher-energy mode and the competitive mode, which is due to the coupling and competition of the quasi-lower-energy effect and the quasi-higher-energy effect. With the increase of the interatomic distance, peaks of the absorption spectra are all red-shifted and the evolutionary trend is also discussed.     

分子轨道波函数相对论效应的高分辨电子动量谱学观测

利用新研制的能量分辨为0.5 eV 的高分辨(e, 2e)谱仪测量了CF3I分子在9-15 eV能区的束缚能谱.新谱仪能较好地分辨该分子碘孤对轨道的自旋轨道劈裂组分5e3/2和5e1/2,并得到了它们各自的电子动量分布以及分支比随动量的变化关系.实验结果清楚地显示了5e3/2和5e1/2态波函数的相对论效应.这是第一个分子轨道波函数相对论效应的直接实验观测.     

分子轨道波函数相对论效应的高分辨电子动量谱学观测

利用新研制的能量分辨为0.5 eV 的高分辨(e, 2e)谱仪测量了CF3I分子在9—15 eV能区的束缚能谱.新谱仪能较好地分辨该分子碘孤对轨道的自旋轨道劈裂组分5e3/2和5e1/2,并得到了它们各自的电子动量分布以及分支比随动量的变化关系.实验结果清楚地显示了5e3/2和5e1/2态波函数的相对论效应.这是第一个分子轨道波函数相对论效应的直接实验观测.     

Direct observation of strain-induced change in surface electronic structure

We have observed a novel modification of a surface state due to a local strain field induced by a nanopattern formation. N adsorption on the Cu(100) surface induces a nanoscale grid pattern, where the clean Cu regions remain periodically. The lattice is contracted on the clean region by adjacent c(2 x 2)N domains, which have a larger lattice constant. On this patterned surface, we have investigated the Tamm-type surface state at M by means of angle-resolved ultraviolet photoelectron spectroscopy. The binding energy of the Tamm state shifts toward the Fermi level continuously with increasing N coverage, i.e., the intensity of the strain field. This behavior due to the strain field is completely different from that caused by electron confinement observed on vicinal surfaces. The Brillouin zone extension corresponding to the lattice contraction was also detected.     

The dynamics of small excitable ion channel clusters

Through computational modeling we predict that small sodium ion channel clusters on small patches of membrane can encode electric signals most efficiently at certain magic cluster sizes. We show that this effect can be traced back to algebraic features of small integers and are universal for channels with a simple gating dynamics. We further explore physiologic conditions under which such effects can occur.     

Multiscale modeling of electronic excitations in branched conjugated molecules using an exciton scattering approach

The exciton scattering (ES) approach attributes excited electronic states in quasi-1D branched polymer molecules to standing waves of quantum quasiparticles (excitons) scattered at the molecular vertices. We extract their dispersion and frequency-dependent scattering matrices at termini, ortho, and meta joints for pi-conjugated phenylacetylene-based molecules from atomistic time-dependent density-functional theory (TD DFT) calculations. This allows electronic spectra for any structure of arbitrary size within the considered molecular family to be obtained with negligible numerical effort. The agreement is within 10-20 meV for all test cases, when comparing the ES results with the reference TD DFT calculations.     

Direct observation of the two-photon generation of free excitonic molecules in CuCl

Two-photon absorption spectra due to excitonic molecule generation in thin CuCl samples at 4.2°K are directly measured using the intense light from a pulsed, frequency tunable dye laser. One narrow induced absorption peak is observed at 3893 Å. This peak exhibits a Fano interference line profile at low laser light intensities. High laser light flux densities result in a saturation, broadening, and blue shift of the induced absorption peak. The maximum value of the two-photon absorption cross section is directly measured to be 2 x 10^-43 cm⁴ sec, and the binding energy of the molecule is found to be 39 meV.