Autoionizing states and their relevance in electron-ion recombination

Atomic physics plays an important role in determining the evolution stages in a wide range of laboratory and cosmic plasmas. Therefore, the main contribution to our ability to model, infer and control plasma sources is the knowledge of underlying atomic processes. Of particular importance are reliable low temperature dielectronic recombination (DR) rate coefficients. This thesis provides systematically calculated DR rate coefficients of lithium-like beryllium and sodium ions via ∆n = 0 doubly excited resonant states. The calculations are based on complex-scaled relativistic many-body perturbation theory in an all-order formulation within the single- and double-excitation coupled-cluster scheme, including radiative corrections. Comparison of DR resonance parameters (energy levels, autoionization widths, radiative transition probabilities and strengths) between our theoretical predictions and the heavy-ion storage rings experiments (CRYRING-Stockholm and TSRHeidelberg) shows good agreement. The intruder state problem is a principal obstacle for general application of the coupled-cluster formalism on doubly excited states. Thus, we have developed a technique designed to avoid the intruder state problem. It is based on a convenient partitioning of the Hilbert space and reformulation of the conventional set of pairequations. The general aspects of this development are discussed, and the effectiveness of its numerical implementation (within the non-relativistic framework) is selectively illustrated on autoionizing doubly excited states of helium.

Innovative Homogeneous and Heterogeneous Systems for Electrochemically Generated Luminescence Investigations: Towards One-Dimensional ECL

My research PhD work is focused on the Electrochemically Generated Luminescence (ECL) investigation of several different homogeneous and heterogeneous systems. ECL is a redox induced emission, a process whereby species, generated at electrodes, undergo a high-energy electron transfer reaction to form excited states that emit light. Since its first application, the ECL technique has become a very powerful analytical tool and has widely been used in biosensor transduction. ECL presents an intrinsically low noise and high sensitivity; moreover, the electrochemical generation of the excited state prevents scattering of the light source: for all these characteristics, it is an elective technique for ultrasensitive immunoassay detection. The majority of ECL systems involve species in solution where the emission occurs in the diffusion layer near to the electrode surface. However, over the past few years, an intense research has been focused on the ECL generated from species constrained on the electrode surface. The aim of my work is to study the behavior of ECL-generating molecular systems upon the progressive increase of their spatial constraints, that is, passing from isolated species in solution, to fluorophores embedded within a polymeric film and, finally, to patterned surfaces bearing “one-dimensional” emitting spots. In order to describe these trends, I use different “dimensions” to indicate the different classes of compounds. My thesis was mostly developed in the electrochemistry group of Bologna with the supervision of Prof Francesco Paolucci and Dr Massimo Marcaccio. With their help and also thanks to their long experience in the molecular and supramolecular ECL fields and in the surface investigations using scanning probe microscopy techniques, I was able to obtain the results herein described. Moreover, during my research work, I have established a new collaboration with the group of Nanobiotechnology of Prof. Robert Forster (Dublin City University) where I spent a research period. Prof. Forster has a broad experience in the biomedical field, especially he focuses his research on film surfaces biosensor based on the ECL transduction. This thesis can be divided into three sections described as follows: (i) in the fist section, homogeneous molecular and supramolecular ECL-active systems, either organic or inorganic species (i.e., corannulene, dendrimers and iridium metal complex), are described. Driving force for this kind of studies includes the search for new luminophores that display on one hand higher ECL efficiencies and on the other simple mechanisms for modulating intensity and energy of their emission in view of their effective use in bioconjugation applications. (ii) in the second section, the investigation of some heterogeneous ECL systems is reported. Redox polymers comprising inorganic luminophores were described. In such a context, a new conducting platform, based on carbon nanotubes, was developed aimed to accomplish both the binding of a biological molecule and its electronic wiring to the electrode. This is an essential step for the ECL application in the field of biosensors. (iii) in the third section, different patterns were produced on the electrode surface using a Scanning Electrochemical Microscopy. I developed a new methods for locally functionalizing an inert surface and reacting this surface with a luminescent probe. In this way, I successfully obtained a locally ECL active platform for multi-array application.

Übergangsmomente zwischen angeregten Zuständen mit der RI-CC2-Methode: Implementierung und Anwendung auf Triplett-Excimere

Die Themengebiete dieser Arbeit umfassen sowohl methodische Weiterentwicklungen im Rahmen der ab initio zweiter Ordnungsmethoden CC2 und ADC(2) als auch Anwendungen dieser Weiterentwick-lungen auf aktuelle Fragestellungen. Die methodischen Erweiterungen stehen dabei hauptsächlich im Zusammenhang mit Übergangsmomenten zwischen angeregten Zuständen. Durch die Implementie-rung der selbigen ist nun die Berechnung transienter Absorptionsspektren möglich. Die Anwendungen behandeln vorwiegend das Feld der organischen Halbleiter und deren photo-elektronische Eigen-schaften. Dabei spielen die bislang wenig erforschten Triplett-Excimere eine zentrale Rolle.rnDie Übergangsmomente zwischen angeregten Zuständen wurden in das Programmpaket TUR-BOMOLE implementiert. Dadurch wurde die Berechnung der Übergangsmomente zwischen Zustän-den gleicher Multiplizität (d.h. sowohl Singulett-Singulett- als auch Triplett-Triplett-Übergänge) und unterschiedlicher Multiplizität (also Singulett-Triplett-Übergänge) möglich. Als Erweiterung wurde durch ein Interface zum ORCA Programm die Berechnung von Spin-Orbit-Matrixelementen (SOMEs) implementiert. Des Weiteren kann man mit dieser Implementierung auch Übergänge in offenschaligen Systemen berechnen. Um den Speicherbedarf und die Rechenzeit möglichst gering zu halten wurde die resolution-of-the-identity (RI-) Näherung benutzt. Damit lässt sich der Speicherbedarf von O(N4) auf O(N3) reduzieren, da die mit O(N4) skalierenden Größen (z. B. die T2-Amplituden) sehr effizient aus RI-Intermediaten berechnet werden können und daher nicht abgespeichert werden müssen. Dadurch wird eine Berechnung für mittelgroße Moleküle (ca. 20-50 Atome) mit einer angemessenen Basis möglich.rnDie Genauigkeit der Übergangsmomente zwischen angeregten Zuständen wurde für einen Testsatz kleiner Moleküle sowie für ausgewählte größere organische Moleküle getestet. Dabei stellte sich her-aus, dass der Fehler der RI-Näherung sehr klein ist. Die Vorhersage der transienten Spektren mit CC2 bzw. ADC(2) birgt allerdings ein Problem, da diese Methoden solche Zustände nur sehr unzureichend beschreiben, welche hauptsächlich durch zweifach-Anregungen bezüglich der Referenzdeterminante erzeugt werden. Dies ist für die Spektren aus dem angeregten Zustand relevant, da Übergänge zu diesen Zuständen energetisch zugänglich und erlaubt sein können. Ein Beispiel dafür wird anhand eines Singulett-Singulett-Spektrums in der vorliegenden Arbeit diskutiert. Für die Übergänge zwischen Triplettzuständen ist dies allerdings weniger problematisch, da die energetisch niedrigsten Doppelan-regungen geschlossenschalig sind und daher für Tripletts nicht auftreten.rnVon besonderem Interesse für diese Arbeit ist die Bildung von Excimeren im angeregten Triplettzu-stand. Diese können aufgrund starker Wechselwirkungen zwischen den π-Elektronensystemen großer organischer Moleküle auftreten, wie sie zum Beispiel als organische Halbleiter in organischen Leucht-dioden eingesetzt werden. Dabei können die Excimere die photo-elktronischen Eigenschaften dieser Substanzen signifikant beeinflussen. Im Rahmen dieser Dissertation wurden daher zwei solcher Sys-teme untersucht, [3.3](4,4’)Biphenylophan und das Naphthalin-Dimer. Hierzu wurden die transienten Anregungsspektren aus dem ersten angeregten Triplettzustand berechnet und diese Ergebnisse für die Interpretation der experimentellen Spektren herangezogen. Aufgrund der guten Übereinstimmung zwischen den berechneten und den experimentellen Spektren konnte gezeigt werden, dass es für eine koplanare Anordnung der beiden Monomere zu einer starken Kopplung zwischen lokal angereg-ten und charge-transfer Zuständen kommt. Diese Kopplung resultiert in einer signifikanten energeti-schen Absenkung des ersten angeregten Zustandes und zu einem sehr geringen Abstand zwischen den Monomereinheiten. Dabei ist der angeregte Zustand über beide Monomere delokalisiert. Die star-ke Kopplung tritt bei einem intermolekularen Abstand ≤4 Å auf, was einem typischen Abstand in orga-nischen Halbleitern entspricht. In diesem Bereich kann man zur Berechnung dieser Systeme nicht auf die Förster-Dexter-Theorie zurückgreifen, da diese nur für den Grenzfall der schwachen Kopplung gültig ist.

Femtosecond laser-based investigations of magnetic circular dichroism in near-threshold photoemission

During the last decades magnetic circular dichroism (MCD) has attracted much interest and evolved into various experimental methods for the investigation of magnetic thin films. For example, synchrotron-based X-ray magnetic circular dichroism (XMCD) displays the absolute values of spin and orbital magnetic moments. It thereby benefits from large asymmetry values of more than 30% due to the excitation of atomic core-levels. Similarly large values are also expected for threshold photoemission magnetic circular dichroism (TPMCD). Using lasers with photon energies in the range of the sample work function this method gives access to the occupied electronic structure close to the Fermi level. However, except for the case of Ni(001) there exist only few studies on TPMCD moreover revealing much smaller asymmetries than XMCD-measurements. Also the basic physical mechanisms of TPMCD are not satisfactorily understood. In this work we therefore investigate TPMCD in one- and two-photon photoemission (1PPE and 2PPE) for ferromagnetic Heusler alloys and ultrathin Co films using ultrashort pulsed laser light. The observed dichroism is explained by a non-conventional photoemission model using spin-resolved band-structure calculations and linear response theory. For the two Heusler alloys Ni2MnGa and Co2FeSi we give first evidence of TPMCD in the regime of two-photon photoemission. Systematic investigations concerning general properties of TPMCD in 1PPE and 2PPE are carried out at ultrathin Co films grown on Pt(111). Here, photon-energy dependent measurements reveal asymmetries of 1.9% in 1PPE and 11.7% in 2PPE. TPMCD measurements at decreased work function even yield larger asymmetries of 6.2% (1PPE) and 17% (2PPE), respectively. This demonstrates that enlarged asymmetries are also attainable for the TPMCD effect on Co(111). Furthermore, we find that the TPMCD asymmetry is bulk-sensitive for 1PPE and 2PPE. This means that the basic mechanism leading to the observed dichroism must be connected to Co bulk properties; surface effects do not play a crucial role. Finally, the enhanced TPMCD asymmetries in 2PPE compared to the 1PPE case are traced back to the dominant influence of the first excitation step and the existence of a real intermediate state. The observed TPMCD asymmetries cannot be interpreted by conventional photoemission theory which only considers direct interband transitions in the direction of observation (Γ-L). For Co(111), these transitions lead to evanescent final states. The excitation to such states, however, is incompatible with the measured bulk-sensitivity of the asymmetry. Therefore, we generalize this model by proposing the TPMCD signal to arise mostly from direct interband transitions in crystallographic directions other than (Γ-L). The necessary additional momentum transfer to the excited electrons is most probably provided by electron-phonon or -magnon scattering processes. Corresponding calculations on the basis of this model are in reasonable agreement with the experimental results so that this approach represents a promising tool for a quantitative description of the TPMCD effect. The present findings encourage an implementation of our experimental technique to time- and spatially-resolved photoemission electron microscopy, thereby enabling a real time imaging of magnetization dynamics of single excited states in a ferromagnetic material on a femtosecond timescale.

Hadronic matrix elements in lattice QCD

The lattice formulation of Quantum ChromoDynamics (QCD) has become a reliable tool providing an ab initio calculation of low-energy quantities. Despite numerous successes, systematic uncertainties, such as discretisation effects, finite-size effects, and contaminations from excited states, are inherent in any lattice calculation. Simulations with controlled systematic uncertainties and close to the physical pion mass have become state-of-the-art. We present such a calculation for various hadronic matrix elements using non-perturbatively O(a)-improved Wilson fermions with two dynamical light quark flavours. The main topics covered in this thesis are the axial charge of the nucleon, the electro-magnetic form factors of the nucleon, and the leading hadronic contributions to the anomalous magnetic moment of the muon. Lattice simulations typically tend to underestimate the axial charge of the nucleon by 5 − 10%. We show that including excited state contaminations using the summed operator insertion method leads to agreement with the experimentally determined value. Further studies of systematic uncertainties reveal only small discretisation effects. For the electro-magnetic form factors of the nucleon, we see a similar contamination from excited states as for the axial charge. The electro-magnetic radii, extracted from a dipole fit to the momentum dependence of the form factors, show no indication of finite-size or cutoff effects. If we include excited states using the summed operator insertion method, we achieve better agreement with the radii from phenomenology. The anomalous magnetic moment of the muon can be measured and predicted to very high precision. The theoretical prediction of the anomalous magnetic moment receives contribution from strong, weak, and electro-magnetic interactions, where the hadronic contributions dominate the uncertainties. A persistent 3σ tension between the experimental determination and the theoretical calculation is found, which is considered to be an indication for physics beyond the Standard Model. We present a calculation of the connected part of the hadronic vacuum polarisation using lattice QCD. Partially twisted boundary conditions lead to a significant improvement of the vacuum polarisation in the region of small momentum transfer, which is crucial in the extraction of the hadronic vacuum polarisation.

Ruthenium-based light harvesting complexes

Polypyridylkomplexe von Ruthenium(II) besitzen eine Vielzahl von Anwendungen, z. B. in Farbstoff-sensibilisierten Solarzellen und als Photokatalysatoren. [Ru(bpy)3]2+ ist einer der prominentesten Ruthenium(II)-Komplexe und besitzt langlebige angeregte 3MLCT-Zustände mit einer Lebensdauer von 1 µs und einer Lumineszenz-Quantenausbeute von 10%. [Ru(bpy)3]2+ ist chiral und kann Stereoisomere bilden, wenn die Liganden unsymmetrisch substituiert sind oder im Falle von oligonuklearen rac/meso-Komplexen. Bis-tridentate Komplexe wie [Ru(tpy)2]2+ sind achiral und umgehen damit unerwünschte Stereoisomere. [Ru(tpy)2]2+ besitzt jedoch enttäuschende photophysikalische Eigenschaften mit einer 3MLCT-Lebensdauer von nur etwa 0.2 ns und einer Quantenausbeute von ≤ 0.0007%. Die Anbringung von Substituenten an [Ru(tpy)2]2+ sowie die Aufweitung der Liganden-Bisswinkel auf 90° bewirken deutlich verbesserte Eigenschaften der emittierenden 3MLCT-Zustände. rnDieser Strategie folgend wurden in der vorliegenden Arbeit neue bis-tridentate Ruthenium(II)-Komplexe entwickelt, synthetisiert und charakterisiert. Durch Anbringen von Ester-Substituenten und Verwenden von Liganden mit erweiterten Bisswinkeln konnten 3MLCT-Lebensdauern von bis zu 841 ns und Quantenausbeuten von bis zu 1.1% erreicht werden. Die neuen bis-tridentaten Komplexe weisen eine deutlich erhöhte Photostabilität im Vergleich zu tris-bidentatem [Ru(bpy)3]2+ auf. rnDie Komplexe wurden als Emitter in Licht-emittierenden elektrochemischen Zellen eingebaut und zeigen Elektrolumineszenz mit einer tiefroten Farbe, die bis ins NIR reicht. Ebenso wurden die Komplexe als Lichtsammler in Farbstoff-sensibilisierten Solarzellen getestet und erreichen Licht-zu-Energie-Effizienzen von bis zu 0.26%. rnDinukleare, stereochemisch einheitliche Ruthenium(II)-Komplexe wurden oxidiert um die Metall-Metall-Wechselwirkung zwischen Ru(II) und Ru(III) in der einfach oxidierten Spezies zu untersuchen. Die unterschiedlichen Redoxeigenschaften der beiden Rutheniumzentren in den verwendeten dinuklearen Verbindungen führt zu einer valenzlokalisierten Situation in der keine Metall-Metall-Wechselwirkung beobachtet wird. Ebenso wurde die Oxidation eines einkernigen Ruthenium(II)-Komplexes sowie dessen spontane Rückreduktion untersucht.rnEnergietransfersysteme wurden mittels Festphasensynthese hergestellt. Dabei ist ein Bis(terpyridin)ruthenium(II)-Komplex als Energie-Akzeptor über eine unterschiedliche Anzahl an Glycineinheiten mit einem Cumarin-Chromophor als Energie-Donor verknüpft. Bei einer kleinen Zahl an Glycineinheiten (0, 1) findet effektiver Energietransfer vom Cumarin- zum Ruthenium-Chromophor statt, wogegen bei zwei Glycineinheiten ein effektiver Energietransfer verhindert ist.rnLicht-induzierte Ladungstrennung wurde erreicht, indem Bis(terpyridin)ruthenium(II)-Komplexe als Chromophore in einem Donor-Chromophor-Akzeptor-Nanokomposit eingesetzt wurden. Dabei wurde ein Triphenylamin-enthaltendes Blockcopolymer als Elektronendonor und ZnO-Nanostäbchen als Elektronenakzeptor verwendet. Bei Bestrahlung des Chromophors werden Elektronen in die ZnO-Nanostäbchen injiziert und die Elektronenlöcher wandern in das Triphenylamin-enthaltende Blockcopolymer. rnrn

Using the Franck-Hertz Experiment To Illustrate Quantization Energy States of the Neon Atom by Electron Impact

na provide students with motivation for the study of quantum mechanics. That microscopic matter exists in quantized states can be demonstrated with modem versions of historic experiments: atomic line spectra (I), resonance potentials, and blackbody radiation. The resonance potentials of mercury were discovered by Franck and Hertz in 1914 (2). Their experiment consisted of bombarding atoms by electrons, and detecting the kinetic energy loss of the scattered electrons (3). Prior to the Franck-Hertz experiment, spectroscopic work bv Balmer and Rvdbere revealed that atoms emitted radiatibn at discrete ekergiis. The Franck-Hertz experiment showed directly that auantized enerm levels in an atom are real, not jist optiEal artifacts. atom can be raised to excited states by inelastic collisions with electrons as well as lowered from excited states by emission of photons. The classic Franck-Hertz experiment is carried out with mercury (4-7). Here we present an experiment for the study of resonance potentials using neon.

Highly Efficient IR to NIR Upconversion in Gd2O2S: Er3+ for Photovoltaic Applications

Upconversion (UC) is a promising option to enhance the efficiency of solar cells by conversion of sub-bandgap infrared photons to higher energy photons that can be utilized by the solar cell. The UC quantum yield is a key parameter for a successful application. Here the UC luminescence properties of Er3+-doped Gd2O2S are investigated by means of luminescence spectroscopy, quantum yield measurements, and excited state dynamics experiments. Excitation into the maximum of the 4I15/2 → 4I13/2 Er3+ absorption band around 1500 nm induces very efficient UC emission from different Er3+ excited states with energies above the silicon bandgap, in particular, the emission originating from the 4I11/2 state around 1000 nm. Concentration dependent studies reveal that the highest UC quantum yield is realized for a 10% Er3+-doping concentration. The UC luminescence is compared to the well-known Er3+-doped β-NaYF4 UC material for which the highest UC quantum yield has been reported for 25% Er3+. The UC internal quantum yields were measured in this work for Gd2O2S: 10%Er3+ and β-NaYF4: 25%Er3+ to be 12 ± 1% and 8.9 ± 0.7%, respectively, under monochromatic excitation around 1500 nm at a power of 700 W/m2. The UC quantum yield reported here for Gd2O2S: 10%Er3+ is the highest value achieved so far under monochromatic excitation into the 4I13/2 Er3+ level. Power dependence and lifetime measurements were performed to understand the mechanisms responsible for the efficient UC luminescence. We show that the main process yielding 4I11/2 UC emission is energy transfer UC.

Observation of an Excited B±c Meson State with the ATLAS Detector

A search for excited states of the B ± c meson is performed using 4.9  fb −1 of 7 TeV and 19.2  fb −1 of 8 TeV pp collision data collected by the ATLAS experiment at the LHC. A new state is observed through its hadronic transition to the ground state, with the latter detected in the decay B ± c →J/ψπ ± . The state appears in the m(B ± c π + π − )−m(B ± c )−2m(π ± ) mass difference distribution with a significance of 5.2 standard deviations. The mass of the observed state is 6842±4±5  MeV , where the first error is statistical and the second is systematic. The mass and decay of this state are consistent with expectations for the second S -wave state of the B ± c meson, B ± c (2S) .

Highly sensitive biological and chemical sensors based on reversible fluorescence quenching in a conjugated polymer

The fluorescence of a polyanionic conjugated polymer can be quenched by extremely low concentrations of cationic electron acceptors in aqueous solutions. We report a greater than million-fold amplification of the sensitivity to fluorescence quenching compared with corresponding “molecular excited states.” Using a combination of steady-state and ultrafast spectroscopy, we have established that the dramatic quenching results from weak complex formation [polymer(−)/quencher(+)], followed by ultrafast electron transfer from excitations on the entire polymer chain to the quencher, with a time constant of 650 fs. Because of the weak complex formation, the quenching can be selectively reversed by using a quencher-recognition diad. We have constructed such a diad and demonstrate that the fluorescence is fully recovered on binding between the recognition site and a specific analyte protein. In both solutions and thin films, this reversible fluorescence quenching provides the basis for a new class of highly sensitive biological and chemical sensors.

Fluorescence and photobleaching dynamics of single light-harvesting complexes

Single light-harvesting complexes LH-2 from Rhodopseudomonas acidophila were immobilized on various charged surfaces under physiological conditions. Polarized light experiments showed that the complexes were situated on the surface as nearly upright cylinders. Their fluorescence lifetimes and photobleaching properties were obtained by using a confocal fluorescence microscope with picosecond time resolution. Initially all molecules fluoresced with a lifetime of 1 ± 0.2 ns, similar to the bulk value. The photobleaching of one bacteriochlorophyll molecule from the 18-member assembly caused the fluorescence to switch off completely, because of trapping of the mobile excitations by energy transfer. This process was linear in light intensity. On continued irradiation the fluorescence often reappeared, but all molecules did not show the same behavior. Some LH-2 complexes displayed a variation of their quantum yields that was attributed to photoinduced confinement of the excited states and thereby a diminution of the superradiance. Others showed much shorter lifetimes caused by excitation energy traps that are only ≈3% efficient. On repeated excitation some molecules entered a noisy state where the fluorescence switched on and off with a correlation time of ≈0.1 s. About 490 molecules were examined.

Shedding light on the dark and weakly fluorescent states of green fluorescent proteins

Recent experiments on various similar green fluorescent protein (GFP) mutants at the single-molecule level and in solution provide evidence of previously unknown short- and long-lived “dark” states and of related excited-state decay channels. Here, we present quantum chemical calculations on cis-trans photoisomerization paths of neutral, anionic, and zwitterionic GFP chromophores in their ground and first singlet excited states that explain the observed behaviors from a common perspective. The results suggest that favorable radiationless decay channels can exist for the different protonation states along these isomerizations, which apparently proceed via conical intersections. These channels are suggested to rationalize the observed dramatic reduction of fluorescence in solution. The observed single-molecule fast blinking is attributed to conversions between the fluorescent anionic and the dark zwitterionic forms whereas slow switching is attributed to conversions between the anionic and the neutral forms. The predicted nonadiabatic crossings are seen to rationalize the origins of a variety of experimental observations on a common basis and may have broad implications for photobiophysical mechanisms in GFP.

Femtosecond dynamics of the forbidden carotenoid S1 state in light-harvesting complexes of purple bacteria observed after two-photon excitation

Time-resolved excited-state absorption intensities after direct two-photon excitation of the carotenoid S1 state are reported for light-harvesting complexes of purple bacteria. Direct excitation of the carotenoid S1 state enables the measurement of subsequent dynamics on a fs time scale without interference from higher excited states, such as the optically allowed S2 state or the recently discovered dark state situated between S1 and S2. The lifetimes of the carotenoid S1 states in the B800-B850 complex and B800-B820 complex of Rhodopseudomonas acidophila are 7 ± 0.5 ps and 6 ± 0.5 ps, respectively, and in the light-harvesting complex 2 of Rhodobacter sphaeroides ≈1.9 ± 0.5 ps. These results explain the differences in the carotenoid to bacteriochlorophyll energy transfer efficiency after S2 excitation. In Rps. acidophila the carotenoid S1 to bacteriochlorophyll energy transfer is found to be quite inefficient (φET1 <28%) whereas in Rb. sphaeroides this energy transfer is very efficient (φET1 ≈80%). The results are rationalized by calculations of the ensemble averaged time constants. We find that the Car S1 → B800 electronic energy transfer (EET) pathway (≈85%) dominates over Car S1 → B850 EET (≈15%) in Rb. sphaeroides, whereas in Rps. acidophila the Car S1 → B850 EET (≈60%) is more efficient than the Car S1 → B800 EET (≈40%). The individual electronic couplings for the Car S1 → BChl energy transfer are estimated to be approximately 5–26 cm−1. A major contribution to the difference between the energy transfer efficiencies can be explained by different Car S1 energy gaps in the two species.

Reações fotoinduzidas em alguns complexos de rênio e desenvolvimento de dispositivos moleculares

Neste trabalho foi realizado o estudo do comportamento fotoquímico e fotofísico de complexos mononucleares de rênio do tipo fac-[Re(CO)3(N N)(L)]+(N N = 1,10-fenantrolina, phen, dipirido[3,2-a:2,3-c]fenazina, dppz, L= trans-1,2bis(4-piridil)etileno, trans-bpe, trans-4-estirilpiridina. trans-stpy) e dos complexos binucleares [(CO)3(phen)Re(trans-bpe)Re(phen)(CO)3]2+, [(CO)3(phen)Re(trans-bpe)Fe(CN5]2- e [(phen)(CO)3Re(trans-bpe)Os(terpy)(bpy)]3+. O enfoque principal deste trabalho é a investigação das propriedades fotoquímicas dos complexos fac-[ Re(CO)3(phen)(trans-bpe)]+, fac-[Re(CO)3(phen)(trans-stpy)]+ fac-[Re(CO)3(dppz)(trans-bpe)+ e [(CO)3(phen)Re(trans-bpe)Re(phen)(CO)3]2+. Observou-se que os compostos em solução de acetonitrila, sob irradiação a 313, 334 ou 365 nm, apresentam variação espectral com definição de pontos isosbésticos, resultante do processo de fotoisomerização trans→cis do ligante coordenado trans-piridil etileno. Os rendimentos quânticos, Φ, da reação de fotoisomerização foram calculados com base no decaimento espectral das bandas de absorção das transições eletrônicas. Os valores médios determinados para a fotoisomeriação dos complexos em solução de CH3CN variam de 0,15 - 0,39 sob excitação a 313 nm e de 0,12 - 0,33 sob excitação a 365 nm. As reações de fotoisomerização foram monitoradas também por medidas de emissão e por RMN de 1H. Observou-se um aumento da intensidade de luminescência com o tempo de irradiação dos complexos, consistente com o estado emissivo 3MLCT dπ[(Re)→π*(α-diimina). Após irradiação, as reações de fotoisomerização dos complexos foram monitoradas por RMN de 1H. Os sinais de prótons do isômero trans tiveram um decréscimo gradual, enquanto que a intensidade dos sinais referentes aos prótons da espécie cis aumentaram. Os rendimentos quânticos para o processo de fotoisomerização dos complexos foram calculados através da integração das áreas dos sinais de prótons. Os valores obtidos foram maiores, pelo menos o dobro, que aqueles valores obtidos via espectroscopia UV-Vis. O comportamento fotoquímico dos complexos incorporados em polimetacrilato de metila, PMMA, foi também investigado. A fotólise cios complexos em filmes de PMMA conduz à variação espectral, de absorção e emissão, similar àquela observada em solução de acetonitrila, atribuícla ao processo de fotoisomerização trans → cis do ligante coordenado. Este estudo mostra que a fotoisomerização do ligante coordenado trans-piridil etileno pode ser promovida também em meio rígido. Essa característica. típica de um dispositivo molecular, pode ser convenientemente explorada no desenvolvimento de fotossensores. As medidas de TRIR mostram que o estado excitado de menor energia para o fac-[Re(CO)3(phen)(trans-bpe)+ é o 3ππ*. Para o fac-[Re(CO)3(phen)(cis-bpe)]+ a ordem dos estados excitados aparecem invertidas com o 3MLCT <3ππ*, evidenciado pela emissão do complexo cis à temperatura ambiente. Nas espécies binucleares, [(phen) Re(CO)3(trans-bpe)Os(terpy)(bpy)]3+ e [(CO)3(phen)Re(trans-bpe)Fe(CN)5]2-, a fotoisomerização trans → cis do ligante coordenado trans-bpe, característica da subunidade fac-[Re(CO)3(phen)(trans-bpe)]+, é inibida pela competição de transferência de energia intramolecular. Em meio rígido, em PMMA ou em EPA a 77 K, os máximos de emissão dos complexos fac-[Re(CO)3(phen)(cis-bpe)]+, fac-[Re(CO)3(phen)(cis-stpy)r e [(CO)3(phen)Re(cis-bpe)Re(phen)(CO)3]2+ sofrem um deslocamento hipsocrômico com o aumento da rigidez do meio. As mudanças nas propriedades emissivas, em termos de energia e tempo de vida do estado excitado, são discutidas baseadas no efeito rigidocrômico luminescente. O trabalho mostra uma forma interessante de fotos sensibilizar um substrato orgâmco usando o fato de que a coordenação estende a absorção do ligante a uma região de comprimento de onda maior e promove a fotoisomerização assistida por complexos metálicos em energias menores.

Intra- vs intermolecular photoinduced electron transfer reactions of a macrocyclic donor-acceptor dyad

The synthesis, structural characterization, and photophysical behavior of a 14-membered tetraazamacrocycle with pendant 4-dimethylaminobenzyl (DMAB) and 9-anthracenylmethyl groups is reported (L-3, 6-((9-anthracenylmethyl)amino)-trans-6,13-dimethyl-13-((4-dimethylaminobenzyl)amino)-1,4,8,11-tetraaza-cyclotetradecane). In its free base form, this compound displays rapid intramolecular photoinduced electron transfer (PET) quenching of the anthracene emission, with both the secondary amines and the DMAB group capable of acting as electron donors. When complexed with Zn(II), the characteristic fluorescence of the anthracene chromophore is restored as the former of these pathways is deactivated by coordination. Importantly, it is shown that the DMAB group, which remains uncoordinated and PET active, acts only very weakly to quench emission, by comparison to the behavior of a model Zn complex lacking the pendant DMAB group, [ZnL2](2+) (Chart 1). By contrast, Stern-Volmer analysis of intermolecular quenching of [ZnL2](2+) by N,N-dimethylaniline (DMA) has shown that this reaction is diffusion limited. Hence, the pivotal role of the bridge in influencing intramolecular PET is highlighted.