Post deposition purification of PTCDA thin films

The decomposition of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules during evaporation of unpurified raw material in ultra high vacuum was studied. The fragments were identified by mass spectrometry and the influence of these fragments and further contaminations of the raw material on the electronic structure of PTCDA thin films was measured by photoemission spectroscopy. Annealing of contaminated PTCDA films was tested as cheap and easy to perform method for (partial) post deposition purification of the contaminated films.     

Detection of NO traces Using resonantly enhanced multiphoton ionization: A method for monitoring atmospheric pollutants

Resonantly enhanced multiphoton ionization (REMPI) is proposed as an ultrasensitive detection method forreal-time monitoring of atmospheric pollutants in situ. The technique is demonstrated in the laboratory for NO diluted in pure nitrogen at 560 mbar. The MPI current resulting from (2+1) photon ionization of NO via the resonantC ² H (v=0) state has been measured for several NO concentrations. Detection levels as low as 50 ppt have been obtained.Laboratoire associé à l'Université de Paris-Sud     

Singlet versus triplet dynamics of β-carotene studied by quantum control spectroscopy

Biomolecules very often present complex energy deactivation networks with overlapping electronic absorption bands, making their study a difficult task. This can be especially true in transient absorption spectroscopy when signals from bleach, excited state absorption and stimulated emission contribute to the signal. However, quantum control spectroscopy can be used to discriminate specific electronic states of interest by applying specifically designed laser pulses. Recently, we have shown the control of energy flow in bacterial light-harvesting using shaped pump pulses in the visible and the selective population of pathways in carotenoids using an additional depletion pulse in the transient absorption technique. Here, we apply a closed-loop optimization approach to β-carotene using a spatial light modulator to decipher the energy flow network after a multiphoton excitation with a shaped ultrashort pulse in the near-IR. After excitation, two overlapping bands were detected and identified as the S₁ state and the first triplet state T₁. Using the transient absorption signal at a specific probe delay as feedback, the triplet signal could be optimized over the singlet contribution.     

Repetition rate multipliers for efficient implementation of multiphoton and pump-probe fluorescence microscopy

With the advances in pulsed laser systems, microscopic imaging techniques such as multiphoton and pump-probe fluorescence microscopy have developed into effective tools for investigating intensity and time-resolved phenomena inside biological systems. However, pulsed lasers used in these techniques usually are commercial systems with repetition frequencies of around 80 MHz. While these systems have proven to be adequate for multiphoton and pump-probe microscopic imaging applications, the temporal separation of the laser pulse train (around 12.5 ns) is long compared to the fluorescence lifetimes of many common fluorescence species. In this work, we present the designs of repetition rate multipliers based on passive optical components that can be used to increase the efficiency in multiphoton and pump-probe fluorescence microscopy. Depending on the lifetime of fluorescence molecules under investigation, the passive repetition rate multiplier can increase the duty cycle of multiphoton or pump-probe microscopy up to fourfold.     

Unified theory of bound and scattering molecular Rydberg states as quantum maps

Using a representation of multichannel quantum defect theory in terms of a quantum Poincaré map for bound Rydberg molecules, we apply Jung's scattering map to derive a generalized quantum map, that includes the continuum. We show that this representation not only simplifies the understanding of the method, but moreover produces considerable numerical advantages. Finally we show under what circumstances the usual semi-classical approximations yield satisfactory results. In particular we see that singularities that cause problems in semi-classics are irrelevant to the quantum map.     

Nondispersive two-electron wave packets in driven helium

We provide a detailed quantum treatment of the spectral characteristics and of the dynamics of nondispersive two-electron wave packets along the periodically driven, collinear frozen planet configuration of helium. These highly correlated, long-lived wave packets arise as a quantum manifestation of regular islands in a mixed classical phase space, which are induced by nonlinear resonances between the external driving and the unperturbed dynamics of the frozen-planet configuration. Particular emphasis is given to the dependence of the ionization rates of the wave packet states on the driving field parameters and on the quantum mechanical phase space resolution, preceded by a comparison of 1D and 3D life times of the unperturbed frozen planet. Furthermore, we study the effect of a superimposed static electric field component, which, on the grounds of classical considerations, is expected to stabilize the real 3D dynamics against large (and possibly ionizing) deviations from collinearity. Received 7 November 2002 / Received in final form 2 December 2002 Published online 28 January 2003     

半导体中多光子吸收跃迁速率的全量子理论分析

本文从非线性光学中辐射跃迁速率的表达式出发,在全量子理论下,导出了半导体中任意阶多光子吸收跃迁速率的一般表达式。理论分析结果表明,n光子吸收跃迁速率与光强的n次方和n阶光子相干度成正比。本文在多能带及二能带理论模型下,对多光子吸收跃迁速率的一般表达式进行了化简,并对非线性相互作用项对跃迁速率的贡献,作了讨论。     

Internal Rotation of the Methyl Group in Cations of Toluene Derivatives

The potential of the internal rotation of the methyl group was determined for o-, m-, and p-fluorotoluene cations by pulsed field ionization spectroscopy. The potential of the internal rotational motion was also surveyed for other toluene derivative cations. It was found that the barrier height generally increases by ionization. The increase in the barrier height has been discussed in connection with the reduction of the internal rotational constant B by ionization. The geometrical distortion of the methyl group during the internal rotation has been suggested.     

Experimental evidence of structural transition from fcc to bulk bcc in nanophase metal clusters of (Fe)n, (Cr)n, (Mo)n and (W)n produced by CO2 laser multiphoton decomposition of metal carbonyls

We have produced nanophase metal clusters, (Fe)_n, (Cr)_n, (Mo)_n and (W)_n, by multiphoton decomposition of the corresponding metal carbonyls with a 10.6 μm CO₂ laser in the presence of Ar and SF₆. The size distribution was narrow and the average diameter was 6, 3.5, 2 and 1 nm for Fe, Cr, Mo and W clusters, respectively. The structure was found to be bcc for both Fe and Cr clusters, fcc for Mo clusters, and amorphous for W clusters (note that all the bulk metals have bcc structure). Considering the cluster sizes (9630, 1870, 230 and 30 for Fe, Cr, Mo and W clusters, respectively) estimated from their average diameters, it is likely that there exists a structural transition from fcc to bulk bcc with increasing cluster size in these metal clusters.     

Quantum model of selective multiphoton processes: The role of external (field) and internal (anharmonic coupling) detunings

Quantum equations of motion describing the energy transfer dynamics via intramolecular anharmonic coupling are presented and solved numerically. Dynamical features of the average excitations of a homogeneous system (SF₆) and a heterogeneous system (H/W) are quantitatively discussed in terms of the intramolecular vibrational relaxation (IVR) rates. Possible mechanisms of surface-enhanced desorption via low-power laser radiation are proposed.This work was supported in part by the Office of Naval Research, the Air Force Office of Scientific Research (AFSC), United States Air Force, under Grant AFOSR-82-0046 and the National Science Foundation under Grant No. CHE-8022874Camille and Henry Dreyfus Teacher-Scholar (1975–82)