Vibronic state specific predissociation rates from excited electronic states

It is shown that predissociation can be perceived as a primary process due to the continuum part of a Morse oscillator potential. In the model proposed here internal conversion to the ground state is thus not necessarily the primary process of a consecutive dissociation but may be a simultaneous decay. As a consequence, dissociation rates should show strong variations from specific (ro-) vibrational states of the first excited electronic states that are similar to those known from “pure” internal conversion rates. This behaviour is demonstrated by calculating predissociation rates for the process. Especially the out-of-plane modes seem to play an extraordinary role in the excess energy behaviour of the predissociation rate. At lower excess energies, rates from single vibronic levels with out-of-plane mode characteristics may show an increase by several orders of magnitude. Received: 13 November 1998     

Laser-excited electronic fluorescence: Self-quenching and quenching of CS2 vapour

Summary Using a laser-induced fluorescence technique, we have measured lifetimes of CS₂ as functions of pressure, collecting the emission at various wave-length regions. We have obtained quenching rate constants for pure CS₂ and CS₂ plus CH₃CN and CO₂ as collision partners. When the emission is collected at a very long wave-length, evidence is given of vibrational relaxation in the singlet state which leads to the existence of a low-energy pathway of intersystem crossing. Two different long-lived states are also detected in the wave-length region centred at 5860 ?, one in the low-pressure regime and the other at pressures above 0.2 Torr approximately. Quenching rate constants of triplet CS₂ by CO₂ are about the same for both long-lived states, suggesting that vibrational relaxation could occur in the triplet state as well.

---

Riassunto Usando una tecnica a fluorescenza indotta da laser, sono state misurate le vite medie di CS₂ in funzione della pressione, raccogliendo le emissioni in varie regioni di lunghezza d'onda. Si sono ottenute costanti di spegnimento per CS₂ puro e CS₂ piú CH₃CN e CO₂ come associati nella collisione. Quando si registra emissione a lunghezza d'onda molto grande, si prova l'esistenza di rilassamento vibrazionale nello stato di singoletto che porta all'esistenza di un percorso a bassa energia dell'incrocio intersistemico. Sono anche determinati due differenti stati a lunga vita nella regione di lunghezza d'onda centrata a 5860 ?, uno nel regime di bassa pressione e l'altro approssimativamente a pressione sopra i 0.2 Torr. Le costanti di spegnimento del tripletto CS₂ mediante CO₂ sono quasi le stesse per entrambi gli stati a lunga vita, e ciò suggerisce che il rilassamento vibrazionale potrebbe verificarsi anche nello stato di tripletto.

---

Резюме Используя технику лазера, возбужденного флуоресценцией, мы измеряем времена жизни CS₂, как функцию давления, собирая излучение в различных областях длин волн. Мы получаем постоянные скорости гашения для чистого CS₂ и для CS₂ плюс CH₃CN и CO₂, которые участвуют в соударениях. Когда излучение собирается для очень больших длин волн, то отмечается вибрационная релаксация в синглетном состоянии. Были обнаружены два различных долгоживущих состояния с длиной волны при 5860 ?, одно при низком давлении, а другое при давлениях около 0.2 тор. Постоянные скорости гашения триплетного CS₂, обусловленные CO₂, оказываются примерно одинаковыми для обоих долгоживущих состояний. Этот факт свидетельствует о том, что вибрационная релаксация может иметь место также в триплетном состоянии.

     

Non-linear pressure dependence of A-state fluorescence lifetime of formaldehyde

Fluorescence lifetimes of formaldehyde excited at 352 nm ( A₂ – A₁ 4₀¹ band) were measured as a function of bath gas pressure. He, N₂, O₂, CO₂ and HCHO were investigated for the bath gas and the temperature dependence between 298 and 500 K for N₂ and O₂ bath gases was also examined. It was found that the non-linear pressure dependence of the lifetime is successfully reproduced by the model formula

Tautomer contributions to the near UV spectrum of guanine: towards a refined picture for the spectroscopy of purine molecules

By using depopulation laser techniques, like IR-UV population labeling coupled to mass-selected R2PI detection, we confirm that four tautomers are responsible for the near UV spectroscopy (310-280 nm) of guanine: two enol and two keto forms, each pair having a 7NH and a 9NH form. Besides the UV spectroscopy of each tautomer, additional information on the excited state nature and dynamics is obtained from fluorescence studies. In particular, the quenching of fluorescence beyond 285 nm, the existence of a background absorption, as well as the existence of a strongly red-shifted component in the fluorescence emission provides evidence for a strong electronic mixing in the excited state together with an efficient non-radiative process. The details of these features are found to be tautomer-dependent. Comparison of the present results with literature data on other purine molecules, like adenine or 9-substituted guanines, enables us to propose a new insight on the spectroscopy and dynamics of the purine molecules. First, a large variability of the tautomer distribution in the gas phase is found within the purine family, in particular a molecular change, as simple as a 9-methylation on guanine, can reduce the tautomer distribution to a single species (enol form). Since the absorption spectrum is tautomer-dependent as well as substituent-dependent, it turns out that the tautomer population is one of the major parameters that control the overall shape of the UV spectrum. Second, the excited state model, often evoked in the literature, which involves electronic coupling between excited states of different natures, namely ππ^* and nπ^* states, might account for the present fluorescence measurements on guanine, providing an extensive excited state electronic mixing is assumed for these systems. Received 24 June 2002 Published online 13 September 2002     

The effects of chemical etching of porous silicon on Raman spectra

We have investigated the effects of chemical etching on Raman spectra of porous silicon. The as-anodized porous silicon consisted mainly of crystalline silicon, as indicated by the Raman spectra. The background in the spectrum was strong, indicating that the porous silicon surface was rough due to the presence of pores. When chemical etching was performed five times, the Raman spectrum revealed the presence of spherically shaped nanocrystalline silicon whose diameter was around 3.5 nm. Further chemical etching, however, extinguished the nanocrystallites, in addition to smoothing the surface morphology.     

Dynamical origin of power spectra

We discuss a possible origin of Tsallis’ statistics from the correlation among constituents which reduces the phase space of the system. We also show that a system of coupled linear harmonic oscillators can exhibit a Tsallis-type behavior. This paper is part of the Topical Issue Statistical Power Law Tails in High-Energy Phenomena.     

On the role of secondary interactions in the production of bremsstrahlung spectra from a thick target

Bremsstrahlung emission, or radiation loss, is the dominant mechanism of energy dissipation of electrons at relativistic energies greater than a few MeV when it is subjected to acceleration in the field of the nucleus or of the electrons. In this study, the Monte Carlo calculations for bremsstrahlung spectra have been described for the case of a thick tungsten target with incident electron beams from 10 to 50 MeV, where secondary interactions induced by the electrons and photons in the target, such as energy loss, absorption, scattering, and (e ⁺, e ⁻)-pair production effects, were taken into account. The text was submitted by the authors in English.     

Electronic excitation and singlet-triplet coupling in uracil tautomers and uracil-water complexes

Electronic spectra of uracil in its diketo (lactam) form and five enol (lactim) tautomeric forms have been investigated by means of combined density functional and configuration interaction methods. We have simulated the effects of hydrogen bonding with a protic solvent by recomputing the spectrum of uracil in the presence of two, four, or six water molecules. Geometries of the electronic ground state and several low-lying excited states have been optimized. Spin-orbit coupling has been determined for correlated wavefunctions employing a non-empirical spin-orbit mean-field approach. In accord with experiment, we find the diketo tautomer to be the most stable one. The calculations confirm that the first absorption band arises from the ¹( π↦π^*) S ₀↦S ₂ excitation. The experimentally observed vibrational structure in this band originates from a breathing mode of the six ring. Complexation with water molecules is seen to cause a significant blue shift of n↦π^* excitations while leaving π↦π^* excitations nearly uninfluenced. Computed radiative lifetimes are presented for the experimentally known weak phosphorescence from the π↦π^* excited T₁ state. Among the uracil lactim tautomers, one is particularly interesting from a spectroscopic point of view. In this tautomer, the π↦π^* excitation gives rise to the S₁ state. Received 18 February 2002 / Received in final form 5 June 2002 Published online 13 September 2002     

Analogous negative parity spectra of125Xe and127Xe

The low spin states of the nucleus¹²⁷Xe have been investigated with the (, 2n) reaction by means of in-beam--spectroscopy, using theosiris-cube-spectrometer at the FNTandem accelerator facility of the University of Cologne. In the negative parity system, four excited states for each of the spins 11/2^–.15/2^– and two 5/2^–.9/2^– — states could be established at excitation energies up to 1MeV above the Yrast line. With this new data, we are able to compare the non-Yrast states and their decay properties to the corresponding states of¹²⁵Xe, which had been studied with similar methods in Cologne. The almost one-to-one correspondence between the states of these neighboring neutron-odd nuclei is a clear indication that their excitations at low spin remain collective well above the Yrast line.     

Modelocked quantum dot vertical external cavity surface emitting laser

We report the first successful modelocking of a vertical external cavity surface emitting laser (VECSEL) with a quantum dot (QD) gain region. The VECSEL has a total of 35 QD-layers with an emission wavelength of about 1060 nm. In SESAM modelocked operation, we obtain an average output power of 27.4 mW with 18-ps pulses at a repetition rate of 2.57 GHz. This QD-VECSEL is used as-grown on a 450 μm thick substrate, which limits the average output power.     

Mechanism of fluorescence energy transfer in aqueous solution cadmium sulfide quantum dots

Cadmium sulfide (CdS) quantum dots (QDs) prepared by a convenient chemical method have been characterized using absorption, fluorescence, and photoluminescence excitation techniques. The photoluminescence excitation studies show that there is an electron transfer from the surface adsorbate (thiourea) to CdS QDs in aqueous solution. The excitation band with peak maximum at 5.8 eV is assigned to the electronic transitions in the chemisorbed thiourea, whereas the excitation band between 3.45 and 3.7 eV corresponds to the band-to-band transition within the nanocrystalline CdS host. The absorption spectroscopy of the CdS QD solutions shows a strong absorption peak which is generated from thiourea. The band-edge fluorescence of the CdS QDs has also been investigated. It is shown that the fluorescence property of the CdS QDs can be enhanced by adding cadmium chloride (CdCl₂) solution.     

Refractive index change mechanisms in femtosecond laser written ceramic Nd:YAG waveguides: micro-spectroscopy experiments and beam propagation calculations

The effect that femtosecond laser filamentation has on the refractive index of Nd:YAG ceramics, and which leads to the formation of waveguide lasers, has been studied by micro-spectroscopy imaging, beam propagation experiments and calculations. From the analysis of the Nd³⁺ luminescence and Raman images, two main types of laser induced modifications have been found to contribute to the refractive-index change: (i) a lattice defect contribution localized along the self-focusing volume of the laser pulses, in which lattice damage causes a refractive-index decrease, and (ii) a lattice strain-field contribution around and inside the filaments, in which the pressure-driven variation of the inter-atomic distances causes refractive-index variations. Scanning near-field optical-transmission and end-coupling experiments, in combination with beam propagation calculations, have been used to quantitatively determine the corresponding contribution of each effect to the refractive-index field of double-filament waveguides. Results indicate that the strain-field induced refractive-index increment is the main mechanism leading to waveguiding, whereas the damage-induced refractive-index reduction at filaments leads to a stronger mode confinement.     

Time-dependent exactly solvable models for quantum computing

A time-dependent periodic Hamiltonian admitting exact solutions is applied to construct a set of universal gates for a quantum computer. The time evolution matrices are obtained in an explicit form and used to construct logic gates for computation. A way of obtaining an entanglement operator is discussed, too. The method is based on transformation of soluble time-independent equations into time-dependent ones by employing a set of special time-dependent transformation operators. The text was submitted by the authors in English.     

The structure of28Si above 10 MeV excitation energy II: Assignments of quantum numbers

New assignments of quantum numbers have been obtained for more than 50 levels in²⁸Si between 8953 and 15915 keV excitation energy. They are based on the measurement of -ray angular distributions or anisotropies on 29 resonances of the²⁷Al(p, ) reaction and on the²⁴Mg(a, ) resonance atE =3355 keV. A total of 15 high-spin states withI=5–7 has been obtained and the spectrum ofT=1 states has been identified up to 15915 keV excitation energy and a maximum spinI=6.     

Controlling the energy transfer between near-field optically coupled ZnO quantum dots

We performed time-resolved spectroscopy of ZnO quantum dots (QD), and observed exciton energy transfer and dissipation between QD via an optical near-field interaction. Two different sizes of ZnO QD with resonant energy levels were mixed to test the energy transfer and dissipation using time-resolved photoluminescence spectroscopy. The estimated energy transfer time was 144 ps. Furthermore, we demonstrated that the ratio of energy transfer between the resonant energy states could be controlled.     

High-efficiency,high-speed VCSELs for optical interconnects

High-efficiency, high-speed, tapered-oxide-apertured vertical-cavity surface-emitting lasers (VCSELs) emitting at 980 nm have been demonstrated. By carefully engineering the tapered oxide aperture, the mode volume can be greatly reduced without adding much optical scattering loss for the device sizes of interest. Consequently, these devices can achieve higher bandwidth at lower current and power dissipation. In addition, the parasitics are reduced by implementing deep oxidation layers and an improved p-doping scheme in the top mirror. Our devices show modulation bandwidth exceeding 20 GHz, a record for 980 nm VCSELs. Moreover, 35 Gb/s operation has been achieved at only 10 mW power dissipation. This corresponds to a data-rate/power-dissipation ratio of 3.5 Gbps/mW. Most importantly, our device structure is compatible with existing manufacturing processes and can be easily manufactured in large volume making them attractive for optical interconnects.     

Technical remarks and comments on the UV/IR-mixing problem of a noncommutative scalar quantum field theory

The possibility of a resummation procedure in order to cure the UV/IR-mixing problem of noncommutative field theories is discussed. The method is presented for a scalar φ⁴ theory on Euclidean space. Finally, we sketch the idea of resummation forU(1)-gauge theories.     

Adaptive clustering of a quantum solvent: the LiH+ cation in bosonic helium from stochastic calculations

Calculations of the quantum structures describing the initial solvation shells of bosonic helium atoms around a polar, ionic system like LiH⁺ are reported, together with the corresponding quantum energies. The calculations were carried out using the Diffusion Monte Carlo (DMC) approach and parametric trial functions. Its final radial and angular distributions for clusters of varying size are analysed and discussed. The solvation of this ionic dopant is shown to occur in a way which is strongly affected by the orientational induction forces between the latter molecule and the solvent atoms, indicating the onset of “snowball" structures at the location of the dopant and the clear distinction between “heliophilic" and “heliophobic" regions of microsolvation.     

Conservation laws derived by the Neutral-Action Method

Conservation laws are a recognized tool in physical- and engineering sciences. The classical procedure to construct conservation laws is to apply Noether's Theorem. It requires the existence of a Lagrange-function for the system under consideration. Two unknown sets of functions have to be found. A broader class of such laws is obtainable, if Noether's Theorem is used together with the Bessel-Hagen extension, raising the number of sets of unknown functions to three. By using the recently developed Neutral-Action Method, the same conservation laws can be obtained by calculating only one unknown set of functions. Moreover the Neutral Action Method can also be applied in the absence of a Lagrangian, since only the governing differential equations are required for this procedure. In the paper, an application of this method to the Schr?dinger equation is presented.