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The protonated Schiff-base retinal acts as the chromophore in bacteriorhodopsin as well as in rhodopsin. In both cases, photoexcitation initializes fast isomerization which eventually results in storage of chemical energy or signaling. The details of the photophysics for this important chromophore is still not fully understood. In this study, action-absorption spectra and photoisomerization dynamics of three retinal derivatives are measured in the gas phase and compared to that of the protonated Schiff-base retinal. The retinal derivatives include C-9=C-10 trans-locked, C-13=C-14 trans-locked and a retinal derivative without the beta-ionone ring. The spectroscopy as well as the isomerization speed of the chromophores are altered significantly as a consequence of the steric constraints.

In this work, a theoretical and computational set of tools to study and analyze time-resolved electron dynamics in molecules, under the influence of one or more external pulses, is presented. By coupling electronic-structure methods with the resolution of the time-dependent Schrödinger equation, we developed and implemented the time-resolved induced density of the electronic wavepacket, the time-resolved formulation of the differential projection density of states (ΔPDOS), and of transition contribution map (TCM) to look at the single-electron orbital occupation and localization change in time. Moreover, to further quantify the possible charge transfer, we also defined the energy-integrated ΔPDOS and the fragment-projected TCM. We have used time-dependent density-functional theory (TDDFT), as implemented in ADF software, and the Bethe-Salpeter equation, as provided by MolGW package, for the description of the electronic excited states. This suite of postprocessing tools also provides the time evolution of the electronic states of the system of interest. To illustrate the usefulness of these postprocessing tools, excited-state populations have been computed for HBDI (the chromophore of GFP) and DNQDI molecules interacting with a sequence of two pulses. Time-resolved descriptors have been applied to study the time-resolved electron dynamics of HBDI, DNQDI, LiCN (being a model system for dipole switching upon highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) electronic excitation), and Ag22. The computational analysis tools presented in this article can be employed to help the interpretation of fast and ultrafast spectroscopies on molecular, supramolecular, and composite systems.

From the mid-19th century until the 1980's, frogs and toads provided important research models for many fundamental questions in visual neuroscience. In the present century, they have been largely neglected. Yet they are animals with highly developed vision, a complex retina built on the basic vertebrate plan, an accessible brain, and an experimentally useful behavioural repertoire. They also offer a rich diversity of species and life histories on a reasonably restricted physiological and evolutionary background. We suggest that important insights may be gained from revisiting classical questions in anurans with state-of-the-art methods. At the input to the system, this especially concerns the molecular evolution of visual pigments and photoreceptors, at the output, the relation between retinal signals, brain processing and behavioural decision-making.

Dr. Kletz is one the pioneers in the process safety area, known widely for his work on inherent safety design and loss prevention. He worked 38 years in Imperial Chemical Industries, and became a fulltime researcher only after his retirement. He published more than 200 papers and 15 books during his retirement. The intellectual basis analysis presented in this article shows that he frequently cited his books in his articles, indicating that his industrial experience was very influential to his scholarly contributions. Lawley, H.G. was one of the researchers whose work had most influence on Kletz's research. Among Dr. Kletz's publications, the article ‘What You Don't Have, Can't Leak’ has the highest impact, while his most influential book is ‘Process plants: A handbook for inherently safer design’. The references co-citation network is divided in two clearly connected components: his earlier work related to infra-red spectra, and his later work addressing process safety related topics, including inherent safety and hazard and accident analysis. Both his work and that of his followers is rooted in a similar intellectual basis within process safety research, in which particularly Dr. Kletz's earlier work forms an influential original body of knowledge rooted in his industrial experience. His career is a prime example of how process safety research has been strongly influenced by knowledge from industrial practice, illustrating that a continued strong connection between industry and academia can lead to very fruitful outcomes. It is hoped that the presented analysis can inspire especially young graduates with academic interests to first embark on an industrial career to gain industrial experience before aiming to contribute to academic process safety knowledge.

While x-ray absorption spectroscopy is mainly governed by electric-dipole transitions, the technique of nonresonant inelastic x-ray scattering (NIXS) offers the possibility to explore higher-order multipole transitions. These transitions obey different selection rules that can reach final states of higher angular momenta, opening complementary spectroscopic perspectives. Here, we investigate the suitability of NIXS to study transuranium compounds. We show that the $K$ edge of the Be encapsulation can be practically fully excluded by using the imaging capabilities of the technique arising from the position of the signals on the multidetector. Experimental results for the multipole transitions at the actinide ${O}_{4,5}$ edges (90--120 eV) in ${\mathrm{UO}}_{2}$, ${\mathrm{NpO}}_{2}$, ${\mathrm{PuO}}_{2}$, and ${\mathrm{Pu}}_{2}{\mathrm{O}}_{3}$ are compared with multielectronic calculations. The spectral features are shown to be very sensitive to the ratio of the triakontadipole and octupole transitions, which could potentially be used to assess the radial expansion of the $5f$ wave function, which is expected to occur in covalent mixing with the O $2p$ states.

A molecule's color is governed by the nature of its electronic transitions. Herein we show that the degree of charge transfer can be assessed by measuring the change in absorption induced by complexation with the betaine zwitterion. Our approach benefits from direct formation of complexes by electrospray of a mixture solution, followed by photodissociation action spectroscopy. We explored two ion groups: 1) No permanent dipole moment due to even charge delocalization (e.g. MnO4- ) and 2) Non-even charge distribution but where the charge according to resonance forms is either delocalized (e.g. oxyluciferin) or located at one site (e.g. m-nitrophenolate, mNP). The maximal shift for ions from (1) was

A detailed computational characterization of the one-photon absorption spectrum of a 2-((E)-2-[ 2,2']-bithiophenyl-5-yl-vinyl)-1-methyl-quinolinium cation in acetonitrile solution is presented. The main physico-chemical effects (solvation, vibronic progression) affecting the band position and shape are progressively introduced in the computational model, highlighting their relative role in the spectral profile. The reported results underline how an accurate reproduction of the experimental spectrum can only be obtained by going beyond oversimplified methods. Moreover, the deep interplay between the solvent effects and nuclear rearrangements permits the negative solvatochromism exhibited by hypsochromic molecules to be explained. This illustrates the potential of the computational investigation, which can shed light on the information hidden in experimental spectra.

Oxygen vacancies are ubiquitous in metal oxides and critical to performance, yet the impact of these states upon charge carrier dynamics important for photoelectrochemical and photocatalytic applications, remains contentious and poorly understood. A key challenge is the unambiguous identification of spectroscopic fingerprints which can be used to track their function. Herein, we employ five complementary techniques to modulate the electronic occupancy of states associated with oxygen vacancies in situ in BiVO4 photoanodes, allowing us to identify a spectral signature for the ionisation of these states. We obtain an activation energy of ̴ 0.2 eV for this ionisation process, with thermally activated electron de-trapping from these states determining the kinetics of electron extraction, consistent with improved photoelectrochemical performance at higher temperatures. Bulk, un-ionised states however, function as deep hole traps, with such trapped holes being energetically unable to drive water oxidation. These observations help address recent controversies in the literature over oxygen vacancy function, providing new insights into their impact upon photoelectrochemical performance.

Both nuclear and electronic dynamics contribute to protein function and need multiple and complementary techniques to reveal their ultrafast structural dynamics response. Real-space information obtained from the measurement of electron density dynamics by X-ray crystallography provides aspects of both, while the molecular physics of coherence parameters and frequency-frequency correlation needs spectroscopy methods. Ultrafast pump-probe applications of protein dynamics in crystals provide real-space information through direct X-ray crystallographic structure analysis or through structural optical crystallographic analysis. A discussion of methods of analysis using ultrafast macromolecular X-ray crystallography and ultrafast nonlinear structural optical crystallography is presented. The current and future high repetition rate capabilities provided by X-ray free electron lasers for ultrafast diffraction studies provide opportunities for optical control and optical selection of nuclear coherence which may develop to access higher frequency dynamics through improvements of sensitivity and time resolution to reveal coherence directly. Specific selection of electronic coherence requires optical probes, which can provide real-space structural information through photoselection of oriented samples and specifically in birefringent crystals. Ultrafast structural optical crystallography of photosynthetic energy transfer has been demonstrated, and the theory of two-dimensional structural optical crystallography has shown a method for accessing the structural selection of electronic coherence.

International audience; Three new linearly arranged bichromophoric systems 1–3 have been prepared, and their photophysical properties have been studied, taking also advantage of femtosecond pump–probe transient absorption spectroscopy. The three compounds contain the same chromophores, that is a Ru(II)-terpy-like species and a fused expanded bipyridinium (FEBP) unit, separated by three different, variously methylated biphenylene-type bridges. The chromophores have been selected to be selectively addressable, and excitation involving the Ru-based or the FEBP-based dyes results in different excited-state decays. Upon Ru-based excitation at 570 nm, oxidative photoinduced electron transfer (OPET) takes place in 1–3 from the 3MLCT state; however, the charge-separated species does not accumulate, indicating that the charge recombination rate constant exceeds the OPET rate constant. Upon excitation of the organic dye at 400 nm, the FEBP-based 1π–π* level is prepared, which undergoes a series of intercomponent decay events, including (i) electron-exchange energy transfer leading to the MLCT manifold (SS-EnT), which successively decays according to 570 nm excitation, and (ii) reductive photoinduced electron transfer (RPET), leading to the preparation of the charge-separated (CS) state. Reductive PET, involving the FEBP-based singlet state, is much faster than oxidative PET, involving the MLCT triplet state, essentially because of driving force reasons. The rate constant of CR is intermediate between the rate constants of OPET and RPET, and this makes 1–3 capable to selectively read the 400 nm excitation as an active input to prepare the CS state, whereas excitation at wavelengths longer than 480 nm is inefficient to accumulate the CS state. Moreover, intriguing differences between the rate constants of the various processes in 1–3 have been analyzed and interpreted according to the superexchange theory for electron transfer. This allowed us to uncover the role of the electron-transfer and hole-transfer superexchange pathways in promoting the various intercomponent photoinduced decay processes occurring in 1–3.

We present ground and excited state frequency calculations of the recently discovered extremely red-shifted chlorophyll f. We discuss the experimentally available vibrational mode assignments of chlorophyll f and chlorophyll a which are characterised by particularly large downshifts of 131-keto mode in the excited state. The accuracy of excited state frequencies and their displacements are evaluated by the construction of Franck&ndash, Condon (FC) and Herzberg&ndash, Teller (HT) progressions at the CAM-B3LYP/6-31G(d) level. Results show that while CAM-B3LYP results are improved relative to B3LYP calculations, the displacements and downshifts of high-frequency modes are underestimated still, and that the progressions calculated for low temperature are dominated by low-frequency modes rather than fingerprint modes that are Resonant Raman active.

The heat flux across the core-mantle boundary (Q(CMB)) is the key parameter to understand the Earth's thermal history and evolution. Mineralogical constraints of the Q(CMB) require deciphering contributions of the lattice and radiative components to the thermal conductivity at high pressure and temperature in lower mantle phases with depth-dependent composition. Here we determine the radiative conductivity (k(rad)) of a realistic lower mantle (pyrolite) in situusing an ultra-bright light probe and fast time-resolved spectroscopic techniques in laser-heated diamond anvil cells. We find that the mantle opacity increases critically upon heating to similar to 3000 K at 40-135 GPa, resulting in an unexpectedly low radiative conductivity decreasing with depth from similar to 0.8 W/m/K at 1000 km to similar to 0.35 W/m/K at the CMB, the latter being similar to 30 times smaller than the estimated lattice thermal conductivity at such conditions. Thus, radiative heat transport is blocked due to an increased optical absorption in the hot lower mantle resulting in a moderate CMB heat flow of similar to 8.5 TW,on the lower end of previous Q(CMB) estimates based on the mantle and core dynamics. This moderate rate of core cooling implies an inner core age of about 1 Gy and is compatible with both thermally- and compositionally-driven ancient geodynamo. (C) 2020 Elsevier B.V. All rights reserved.

The Operational Land Imager (OLI) onboard Landsat 8 has found successful application in inland and coastal water remote sensing. Its radiometric specification and high spatial resolution allows quantification of water-leaving radiance while resolving small water bodies. However, its limited multispectral band set restricts the range of water quality parameters that can be retrieved. Identification of cyanobacteria biomass has been demonstrated for sensors with a band centered near 620 nm, the absorption peak of the diagnostic pigment phycocyanin. While OLI lacks such a band in the orange region, superposition of the available multispectral and panchromatic bands suggests that it can be calculated by a scaled difference. A set of 428 in situ spectra acquired in diverse lakes in Belgium and The Netherlands was used to develop and test an orange contra-band retrieval algorithm, achieving a mean absolute percentage error of 5.39% and a bias of −0.88% in the presence of sensor noise. Atmospheric compensation error propagated to the orange contra-band was observed to maintain about the same magnitude (13% higher) observed for the red band and thus results in minimal additional effects for possible base line subtraction or band ratio algorithms for phycocyanin estimation. Generality of the algorithm for different reflectance shapes was tested against a set of published average coastal and inland Optical Water Types, showing robust retrieval for all but relatively clear water types (Secchi disk depth > 6 m and chlorophyll a < 1.6 mg m − 3 ). The algorithm was further validated with 79 matchups against the Ocean and Land Colour Imager (OLCI) orange band for 10 globally distributed lakes. The retrieved band is shown to convey information independent from the adjacent bands under variable phycocyanin concentrations. An example application using Landsat 8 imagery is provided for a known cyanobacterial bloom in Lake Erie, US. The method is distributed in the ACOLITE atmospheric correction code. The contra-band approach is generic and can be applied to other sensors with overlapping bands. Recommendations are also provided for development of future sensors with broad spectral bands with the objective to maximize the accuracy of possible spectral enhancements.

International audience; We present optical absorption spectra from the ultraviolet to the visible for size selected neutral Agn clusters (n = 5–120) embedded in solid Ne. We compare the spectra to time-dependent density functional calculations (TDDFT) that address the influence of the Ne matrix. With increasing size, several highly correlated electron excitations gradually develop into a single surface plasmon. Its energy is situated between 3.9 and 4.1 eV and varies with size according to the spherical electronic shell model. The plasmon energy is highest for clusters with atom numbers fully filling states with the lowest radial quantum number (e.g. 1s, 1p, 1d,...). TDDFT calculations for clusters with several candidate geometrical structures embedded in Ne show excellent agreement with the experimental data, demonstrating that the absorption bands depend only weakly on the exact structure of the cluster.

Accurate characterization of the high-lying excited state manifolds of organic molecules is of fundamental importance for the interpretation of the rich response detected in time-resolved nonlinear electronic spectroscopies. Here, we have characterized the singlet excited state manifold of benzophenone (BP), a versatile organic photoinitiator and a well-known DNA photosensitizer. Benchmarks of various multiconfigurational/multireference (RASSCF/PT2) and time-dependent density functional theory (TD-DFT) approaches allowed assignments of experimental linear absorption signals of BP in the ultraviolet (UV) region, with unprecedented characterization of ground state absorptions in the far UV. Experimental transient absorption spectra obtained by UV-vis pump-probe spectroscopy at very short time delays are shown to be directly comparable to theoretical estimates of excited state absorptions (from the low-lying nOπ∗ and π π∗ singlet states) in the Franck-Condon region. Multireference computations provided reliable interpretation of the PP spectra, with TD-DFT results yielding a fair agreement as long as electronic transitions featuring double excitations contributions are not involved. These results lay the groundwork for further computational studies and interpretation of experimental nonlinear electronic spectra of benzophenone in more complex systems, such as BP/DNA adducts.

We study the absorption spectra of the yellow excitons in Cu$_2$O in high magnetic fields using polarization-resolved optical absorption measurements with a high frequency resolution. We show that the symmetry of the yellow exciton results in unusual selection rules for the optical absorption of polarized light and that the mixing of ortho- and para- excitons in magnetic field is important. Our calculation of the energies of the yellow exciton series in an arbitrary magnetic field gives an excellent fit to experimental data and allows us to understand the complex structure of excitonic levels and their magnetic field dependence, which resolves the old-standing disagreement between the results of optical absorption and cyclotron resonance measurements., 19 pages, 5 figures

In this paper we present a detailed computational study of the electronic structure and optical properties of triply-bonded hydrocarbons with linear, and graphyne substructures, with the aim of identifying their potential in opto-electronic device applications. For the purpose, we employed a correlated electron methodology based upon the Pariser-Parr-Pople model Hamiltonian, coupled with the configuration interaction (CI) approach, and studied structures containing up to 42 carbon atoms. Our calculations, based upon large-scale CI expansions, reveal that the linear structures have intense optical absorption at the HOMO-LUMO gap, while the graphyne ones have those at higher energies. Thus, the opto-electronic properties depend on the topology of the {graphyne substructures, suggesting that they can be tuned by means of structural modifications. Our results are in very good agreement with the available experimental data., Comment: main text 29 pages + 4 figures + 1 TOC graphic (included), supporting information 21 pages

In this paper we studied the structural, vibrational and electronic properties of the 4'-bromomethyl-2-biphenylcarbonitrile (BMBP) 4'-chloromethyl-2-biphenylcarbonitrile (CMBP) and 4'-fluoromethyl-2-biphenylcarbonitrile (FMBP) compounds using experimental and theoretical methods. The FT-IR and FT-Raman spectra of BMBP in solid phase were recorded in the region 4000-400 cm(-1) and 4000 -50 cm(-1), respectively. The UV absorption spectrum of BMBP was recorded in dichloromethane and methanol solvents in the range 180-400 nm. The theoretical spectral properties of title compounds were simulated using density functional theory (DFT) and time dependent DFT methods. Scaling of the vibrational frequencies was carried out with the MOLVIB program using multiple scaling factors and assignment to each vibrational frequency was consigned on the basis of potential energy distribution (PED). The electronic spectrum of BMBP in two different solvents (methanol and dichloromethane), calculated at the CAM-B3LYP/6-31G(d,p) level compares well with the experimental data and validates the current method for predicting the absorption spectrum of CMBP and FMBP. Furthermore, the electronic, nonlinear optical and thermodynamics properties of the three compounds were discussed in detailed. (C) 2017 Elsevier B.V. All rights reserved.

There is an increasing level of interest in the use of black TiO2 prepared by thermal hydrogen treatments (H:TiO2) due to the potential to enhance both the photocatalytic and the light-harvesting properties of TiO2. Here, we examine oxygen-deficient H:TiO2 nanotube arrays that have previously achieved very high solar-to-hydrogen (STH) efficiencies due to incident photon-to-current efficiency (IPCE) values of >90% for photoelectrochemical water splitting at only 0.4 V vs RHE under UV illumination. Our transient absorption (TA) mechanistic study provides strong evidence that the improved electrical properties of oxygen-deficient TiO2 enables remarkably efficient spatial separation of electron–hole pairs on the submicrosecond time scale at moderate applied bias, and this coupled to effective suppression of microsecond to seconds charge carrier recombination is the primary factor behind the dramatically improved photoelectrochemical activity.

Accurate ab initio modeling of spectroscopic signals in nonlinear electronic spectra, such as bidimensional (2D) spectra, requires the computation of the electronic transitions induced by the incoming pump/probe pulses, resulting in a challenging calculation of many electronic excited states. A protocol is thus required to evaluate the variations of spectral properties, like transition energies and dipole moments, with the computational level, and to estimate the sensitivity of the spectra to these variations. Such a protocol is presented here within the framework of complete and restricted active space self-consistent field (CASSCF/RASSCF) theory and its second-order perturbation theory extensions (CASPT2/RASPT2). The electronic excited-state manifolds of pyrimidine nucleobases (thymine, uracil, and cytosine) are carefully characterized in vacuo employing high-level RAS(0,0|10,8|2,12)//SS-RASPT2 calculations. The results provide a reference data set that can be used for optimizing computational efforts and costs, as required for studying computationally more demanding multichromophoric systems (e.g., di- and oligonucleotides). The spectroscopic signatures of the 2D electronic spectrum of a perfectly stacked uracil–cytosine dimer model are characterized, and experimental setups are proposed that can resolve non-covalent interchromophoric interactions in canonical pyrimidine nucleobase-stacked dimers.

International audience; In this paper, we prepared and studied sensors based on Molecular Semiconductor-Doped Insulator (MSDI) heterojunctions. These original devices are built with two stacked layers of molecular materials and exhibit very specific electrical and sensing properties. We studied the properties of a MSDI composed of the perylenetetracarboxylic dianhydride, PTCDA, or the fluorinated perylenebisimine derivative, C4F7-PTCDI, as n-type molecular material sublayers, and LuPc2 as a p-type semiconductor top layer. Their response to ammonia was compared to that of a resistor formed of only the top layer of the MSDI (LuPc2). Ammonia increases the current in the MSDIs whereas it causes a decrease in the case of LuPc2 resistors, as previously observed for other MSDIs with a n-type sublayer. At first, we showed the significant effect of the applied potential on the response of these sensors. There is an optimum operating point for which the response to ammonia is maximized, which depends on the nature of the samples. The influence of the thickness of the layers was studied, showing a strong influence of this parameter on the sensing properties. MSDIs prepared with fluorinated PTCDI exhibit a higher energy barrier and a lower current. Finally, in general, PTCDA/LuPc2 MSDIs show a strong response to ammonia with a response up to 250% to 30 ppm NH3 at 50% of relative humidity for the MSDI PTCDA/LuPc2 50 nm/50 nm. A discrimination better than 10 ppm between the ammonia concentrations was observed, regardless of relative humidity between 10 and 70% rh.

Car−Parrinello structural optimizations of realistic models of the Maya Blue (MB) hybrid material are combined with TDDFT calculations of the electronic excitation spectra to identify the nature of the fundamental guest−host interactions leading to the unusual stability of this pigment. The comparison with the features of the experimental visible spectrum reveals that the main mode of interaction between the host solid (the palygorskite clay) and the guest molecule (the organic indigo dye) involves the coordination of the carbonyl group of the dye by Al3+ ions exposed at the edge of the palygorskite tunnels. Analogous Mg2+−dye interactions which do not strongly affect the MB visible spectrum can also be present. Thermal treatment used in the preparation of the pigment appears therefore essential to release some of the structural water molecules tightly bound to the Al3+ ions in the internal clay surface, thus leaving them available to coordinate the organic molecule. Moderate heating also favors the oxida...

Modifications of the optical properties of poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] induced by fluorination of the vinylene units are investigated by means of time dependent density functional theory (TD-DFT) calculations and spectroscopic measurements in solution. The energy of the main absorption peak is blue-shifted by more than 0.8 eV in the fluorinated polymers. TD-DFT excitation energies for non-fluorinated and fluorinated oligomer structures of increasing number of monomers, employing fully relaxed geometries, are compared to the experimental absorption energies of the polymers. We found that the measured large blue-shift induced by the fluorination of the vinylene units is not caused by the electron-withdrawing effect of the fluorine substituents but it is related to a steric effect. The inter-monomer torsional angle of the fluorinated structures increases above 50 degrees , while in the non-fluorinated systems it is below 20 degrees . Further insight into the origin of the large blue-shift of the excitation energies is gained by a detailed analysis of the torsional potentials of non-fluorinated and fluorinated dihydroxystilbene. While for planar geometries the energy gap increases due to fluorination, it decreases for highly distorted geometries. In addition, we found that the torsional potential of dihydroxystilbene is rather flat, meaning that different isomers might, e.g., in the solid state, coexist.

New photoelectron, ultraviolet (UV), and vacuum UV (VUV) spectra have been obtained for bromobenzene by synchrotron study with higher sensitivity and resolution than previous work. This, together with use of ab initio calculations with both configuration interaction and time dependent density functional theoretical methods, has led to major advances in interpretation. The VUV spectrum has led to identification of a considerable number of Rydberg states for the first time. The Franck-Condon (FC) analyses including both hot and cold bands lead to identification of the vibrational structure of both ionic and electronically excited states including two Rydberg states. The UV onset has been interpreted in some detail, and an interpretation based on the super-position of FC and Herzberg-Teller contributions has been performed. In a similar way, the 6 eV absorption band which is poorly resolved is analysed in terms of the presence of two pi pi* states of (1)A(1) (higher oscillator strength) and B-1(2) (lower oscillator strength) symmetries, respectively. The detailed analysis of the vibrational structure of the 2(2)B(1) ionic state is particularly challenging, and the best interpretation is based on equation-of-motion-coupled cluster with singles and doubles computations. A number of equilibrium structures of the ionic and singlet excited states show that the molecular structure is less subject to variation than corresponding studies for iodobenzene. The equilibrium structures of the 3b(1)3s and 6b(2)3s (valence shell numbering) Rydberg states have been obtained and compared with the corresponding ionic limit structures. (C) 2015 AIP Publishing LLC.

First-principles simulations of two-dimensional electronic spectroscopy in the ultraviolet region (2DUV) require computationally demanding multiconfigurational approaches that can resolve doubly excited and charge transfer states, the spectroscopic fingerprints of coupled UV-active chromophores. Here, we propose an efficient approach to reduce the computational cost of accurate simulations of 2DUV spectra of benzene, phenol, and their dimer (i.e., the minimal models for studying electronic coupling of UV-chromophores in proteins). We first establish the multiconfigurational recipe with the highest accuracy by comparison with experimental data, providing reference gas-phase transition energies and dipole moments that can be used to construct exciton Hamiltonians involving high-lying excited states. We show that by reducing the active spaces and the number of configuration state functions within restricted active space schemes, the computational cost can be significantly decreased without loss of accuracy in predicting 2DUV spectra. The proposed recipe has been successfully tested on a realistic model proteic system in water. Accounting for line broadening due to thermal and solvent-induced fluctuations allows for direct comparison with experiments.

Three dinuclear iridium(III) complexes consisting of a conjugated bis-tpy type bridging ligand and cyclometallating capping tridentate ligands of the 1,3-di-2-pyridylbenzene family have been prepared (tpy, 2,2',6',2 ''-terpyridine). The two tpy units of the bridge are connected via their back-positions (4') either directly or with a p-phenylene or p-biphenylene spacer. The synthesis relies on the reaction between the dinuclear [Ir(dpb)Cl-2](2) complex (dpb-H) = 1,3-dipyridyl-4,6-dimethylbenzene) and the corresponding bis-tpy ligand. Electrochemical measurements afford metal-centered oxidation and ligand-centered reduction potentials; from the oxidation steps, no evidence is obtained for a strong coupling between the two iridium(III) subunits of the dinuclear species. For all complexes, ground-state absorption data in the 380 nm to visible region show a trend which is consistent with the presence of charge-transfer (CT) transitions involving different degrees of electronic delocalization at the bridging ligands. (dpb)Ir(tpy-tpy)Ir(dpb)(4+) exhibits an appreciable luminescence at room temperature (phi = 3.0 x 10(-3); tau = 3.3 ns), whereas no emission from the other binuclear complexes is detected. All binuclear complexes luminesce at 77 K, and a metal-to-ligand CT nature for (dpb)Ir(tpy-tpy)Ir(dpb)(4+) is suggested, whereas a ligand-centered (LC) emission is proposed for (dpb)Ir(tpy-(ph)(2)-tpy)Ir(dpb)(4+) on the basis of the comparison with the phosphorescence properties of the free bridging ligand, tpy-(ph)2-tpy. Transient absorbance experiments at room temperature afford the absorption spectra and lifetimes of the nonemissive excited states. For (dpb)Ir(tpy-ph-tpy)Ir(dpb)(4+) and (dpb)Ir(tpy-(ph)(2)-tpy)Ir(dpb)(4+), the spectra exhibit a broad profile peaking around 780 nm, quite intense in the case of (dpb)Ir(tpy-(ph)(2)-tpy)Ir(dpb)(4+), and lifetimes of 160 and 440 ps, respectively.

A rare example of dual coordination modes by a novel tridentate ligand gives rise to unique fac-and mer-Ru((II/III)) complexes. The mer-Ru(II)-complex displays the farthest red-shift of a triplet metal-to-ligand charge transfer ((3)MLCT) emission with a tridentate ligand for a mononuclear complex. This observation is a consequence of large bite angle and strong σ-donation by the ligand, the combined effect of which helps to separate the energy of the (3)MLCT and (3)MC states.

A spherical tensor expansion is carried out to express the resonant inelastic scattering cross-section as a sum of products of fundamental spectra with tensors involving wavevectors and polarization vectors of incident and scattered photons. The expression presented in this paper differs from that of the influential article by Carra et al. (Phys. Rev. Lett. 74, 3700, 1995) because it does not omit interference terms between electric dipole and quadrupole contributions when coupling each photon to itself. Some specific cases of the spherical tensor expansion are discussed. For example the case of isotropic samples is considered and the cross-section is expressed as a combination of only three fundamental spectra for the situation where electric dipole or electric quadrupole transitions in the absorption process are followed by electric dipole transitions in the emission. This situation includes the case of untextured powder samples, which corresponds to the most frequent situation met experimentally. Finally, it is predicted that some circular dichroism may be observed on isotropic samples provided that the circular polarization of the scattered beam can be detected.

Ruthenium terpyridine complexes of the type [Ru-II(trpy)(L)(X)][ClO4](n) 1-15 [trpy=2,2':6,2"-terpyridine; L=NC5H4N=NC6H4(R), R=H, m-Me, m-Cl, p-Me or p-Cl; X=Cl-, n=1 (1-5); H2O, n=2 (6-10) or OH-, n=1 (11-15)] have been synthesized. The single crystal structures of 1 and 6 were determined. Complex 4 develops in two possible isomeric forms whereas all other complexes stabilise preferentially in one isomeric form. The complexes exhibit strong MLCT bands near 500 nm and ligand based transitions in the UV region. 1-5 exhibit moderately strong emissions at 77 K near 600 nm. The chloro (1-5) and the hydroxo (11-15) complexes display ruthenium(III)-ruthenium(II) couples and three to four successive one-electron ligand based reductions. The aqua-complexes (6-10) exhibit a reversible 2e(-)/2H(+) single-step oxidation process in the pH range 1-5.5 corresponding to the [Ru-II(trpy)(L)(H2O)](2+)-[Ru-IV(trpy)(L)(O)](2+) couple and the potential decreases linearly with increase in pH. The chemical oxidations of 6-10 by an excess of Ce-IV in 0.5 M H2SO4 also lead to the formation of corresponding [Ru-IV(trpy)(L)(O)](2+). The oxo-complexes are stable only in the presence of an excess of Ce-IV, otherwise they catalyse the oxidation of water to dioxygen and convert back into the parent aqua-species. The pseudo first order rate constant of the process [Ru-IV(trpy)(L)(O)](2+)--> [Ru-II(trpy)(L)(H2O)](2+) has been determined.

WOS:000317352600022; A novel class of luminescent octahedral ruthenium complexes 2-4 displaying a pi-bonded quinonoid ligand is described. Remarkably, the presence of this organometallic ligand affects their UV-vis properties and transforms them into panchromatic absorbers. Furthermore, it turns on room temperature NIR emissions.

We present a computational approach of general applicability to simulate the vibronic line shapes of absorption and electronic circular dichroism (ECD) spectra in rigid exciton-coupled dimers based on a time dependent expression of the spectra and quantum dynamical calculations. We adopt a diabatic model of interacting states localized on the monomers whose electronic potential energy surfaces are described within harmonic approximation, including the effect of displacements, frequency changes, and normal-mode mixings. Spectra that fully account for the effect of all nuclear degrees of freedom of the system are obtained through a hierarchical representation of the Hamiltonian in blocks, defined so that few blocks accurately describe the short time dynamics. of the system. With this approach, on the ground of time dependent density functional theory calculations, we simulate the absorption and ECD spectra of a covalent compound representing a ``dimer'' of anthracene, in the spectral region of the L-1(a) monomer transition, obtaining results in good agreement with the experiment.

This paper develops a theory of resonant Raman scattering within the framework of a localized model. Expressions for the scattering amplitude and cross section are derived by employing the methods of spherical-tensor analysis. a simple factorization is obtained for the geometrical (angular dependence) and electronic (matrix element) components, which can therefore be studied independently. Photon polarization effects are examined. It is shown that, for fast collisions, the integrated intensity is expressible by way of spin and orbital effective operators, thus allowing for a simple interpretation of the scattering process. For the 2p-->4f, 3d-->2p resonance in Gd3+, Dy3+, Ho3+ and Er3+, numerical calculations of the cross section are discussed. In the case gadolinium, the agreement between calculations and experiments provides further evidence for the quadrupolar nature of certain spectral features.

We present a theoretical study of the dispersion of Frenkel-type excitons in the low-temperature Pa(3) over bar phase of solid C-60. Exciton propagation is accomplished by an exchangelike two-step process, where an electron-hole pair on a given C-60 molecule is split by the intermolecular kinetic energy and recombines on a neighboring molecule. We apply our results to the theoretical calculation of the nonlinear optical susceptibility for second-harmonic generation, for which we find reasonable agreement with experiment.

The solvent shift of the π* ← n transition of acetone in water, acetonitrile, and tetrachloromethane was calculated in a combined quantum mechanical—classical mechanical approach, using both dielectric continuum and explicit, polarizable molecular solvent models. The explicit modeling of solvent polarizability allows for a separate analysis of electrostatic, induction, and dispersion contributions to the shifts. The calculations confirm the qualitative theories about the mechanisms behind the blue shift in polar solvents and the red shift in nonpolar solvents, the solvation of the ground state due to electrostatic interactions being preferential in the former, and favorable dispersion interaction with the excited state, in the latter case. Good quantitative agreement for the solvent shift between experiment (+1,700, +400, and −350 cm−1 in water, acetonitrile, and tetrachloromethane, respectively) and the explicit solvent model (+1,821, +922, and −381 cm−1) was reached through a modest Monte Carlo sampling of the solvent degrees of freedom. A consistent treatment of the solvent could only be realized in the molecular solvent model. The dielectric‐only model needs reparameterization for each solvent

We present an x-ray magnetic circular dichroism (XMCD) study of a [Ce(10 \AA{})/Fe(30 \AA{})] multilayer performed at the Ce-${M}_{4,5}$ absorption edges. In this system the Ce-$4f$ electrons are strongly hybridized with the valence band. XMCD experiments show that they carry an ordered magnetic moment. The differences of the shape of the XMCD signals of a typical $\ensuremath{\gamma}$-like compound (CeCuSi) and of the Ce/Fe multilayer highlight the role of hybridization in determining the ground state of cerium atoms in the multilayer, which results in a mixing of $J=\frac{5}{2}$ and $J=\frac{7}{2}$ coupled states.

The electric-dipole-forbidden T-1(1g) excitonic state of solid C-60 at hw=1.81 eV can be probed with a second-harmonic generation (SHG) experiment. We show that the SHG line shape depends strongly on the degree of rotational order. We observe a splitting into two peaks below the rotational ordering phase-transition temperature of 260 K. The origin of this splitting is discussed in terms of a possible Jahn-Teller effect, a possible Davydov splitting due to the four molecules per unit cell in the low-temperature phase, and a mixing of the nearly degenerate T-1(1g) and (1)G(g) free molecule states because of the lower symmetry in the solid. The exciton band structure is calculated with a charge-transfer-mediated propagation mechanism as suggested by Lof et al.(2) and with one-electron (-hole) transfer integrals determined from band-structure calculations. Comparison with our experimental SHG data leads to a reasonable agreement and shows that a mixing of (1)T(1)g and (1)G(g) states may explain the splitting at low temperature.

We present near steady-state photoinduced absorption (PIA) spectroscopy and steady-state light-induced electron spin resonance (LESR) studies on photoinduced electron transfer reactions in composite films of well defined α-oligothiophenes (Tn, n=6, 7, 9, and 11) as electron donor with buckminsterfullerene (C60) and a methanofullerene derivative (1-(3-cholestanoxycarbonyl)propyl-1-phenyl-[6.6]C61) as electron acceptors. Dispersion on a molecular level of these fullerenes in oligothiophene films causes quenching of both the photoluminescence and intersystem crossing after photoexcitation across the π–π* energy gap as a result of a fast electron transfer reaction. The PIA spectra exhibit bands due to Tn+• radical cations, fullerene radical anions and electroabsorption oscillations of the π–π* band edge resulting from strong local electric fields set up by the photoinduced charges. LESR spectra give additional unambiguous evidence of the photoinduced electron transfer reaction. Using PIA and LESR, we do not observe an effect of the conjugation length of the photoinduced electron transfer reaction or on the metastability of the charge-separated state.

Multi-wavelength photometers, blood gas analysers and pulse oximeters are widely used to measure various oxygen-related quantities. The definitions of these quantities are not always correct. This paper gives insight in the various definitions for oxygen quantities. Furthermore, the possible influences of dyshaemoglobins and fetal haemoglobin on the accuracy of pulse oximetry are discussed. As pulse oximeters are constructed for the determination of arterial oxygen saturation, they should be validated with sample oxygen saturation values and not with the oxyhaemoglobin fraction. The influence of carboxyhaemoglobin is insubstantial over an oxygen saturation range of 0% to 100%. Through the presence of methaemoglobin, pulse oximetry will give an underestimation above 70% and an overestimation below 70% oxygen saturation. The influence of fetal haemoglobin is insignificant in the neonatal use of pulse oximetry, in the range of 75% to 100% arterial oxygen saturation. However, a pulse oximeter underestimates the arterial oxygen saturation at the 25% level with 5%, if the pulse oximeter has been calibrated in human adults. Such a low level of arterial oxygen saturation can be present in the fetus during labor.

International audience; Methodological advances in multiple scattering theory (MST) in both wave and Green's function versions are reported for the calculation of electronic ground and excited state properties of condensed matter systems with an emphasis on core-level photoemission and absorption spectra. Full-potential MST is reviewed and extended to non-local potentials. Multichannel MST is reformulated in terms of the multichannel density matrix whereby strong electron correlation of atomic multiplet type can be accounted for in both ground and excited states.

International audience; We report the first visible spectrum of a heme-protein in the gas phase. The aim of this work was to provide a reference for the optical absorption of an isolated heme-protein to better understand the influence of protein conformation and fluctuation and of solvent on its optical properties. After laser irradiation of gas-phase cytochrome c (cyt c), electron emission is observed. Electron photodetachment yield of cyt c 6- was recorded in the region of the Soret band of the porphyrin group, showing a maximum at 410 nm. Our results are compared with optical spectra of gas-phase heme and of cyt c in solution. We discuss the influence of the polypeptide chain and of the solvent on both the position and the broadening of the Soret band. Action spectrum of gas-phase cyt c is close to the absorption of native cyt c in solution, suggesting an efficient protection of the heme group from solvent accessibility by the polypeptide chain and similar interactions between the two moieties in solution and the gas phase.

The dynamics following the photoexcitation of Na and Li atoms located on the surface of helium nanodroplets has been investigated in a joint experimental and theoretical study. Photoelectron spectroscopy has revealed that excitation of the alkali atoms via the (n + 1)s ←ns transition leads to the desorption of these atoms. The mean kinetic energy of the desorbed atoms, as determined by ion imaging, shows a linear dependence on excitation frequency. These experimental findings are analyzed within a three-dimensional, time-dependent density functional approach for the helium droplet combined with a Bohmian dynamics description of the desorbing atom. This hybrid method reproduces well the key experimental observables. The dependence of the observables on the impurity mass is discussed by comparing the results obtained for the (6)Li and (7)Li isotopes. The calculations show that the desorption of the excited alkali atom is accompanied by the creation of highly non-linear density waves in the helium droplet that propagate at supersonic velocities.

The results of a combined experimental and theoretical study of the electronic circular dichroism spectrum of (-)[9] (2,5)Pyridinophane are presented. The features observed in the measured spectrum in the 180350?nm wavelength region are reproduced by a series of calculations carried out within a density functional time-dependent approach, coupled with a vibronic analysis allowing rationalizing unambiguously the chiral response of the molecule. Chirality 24:9941004, 2012. (c) 2012 Wiley Periodicals, Inc.

The combination of photonics and silicon technology is a great challenge because of the potentiality of coupling electronics and optical functions on a single chip. Silicon nanocrystals are promising in various areas of photonics especially for light-emitting functionality and for photovoltaic cells. This review describes the recent achievements and remaining challenges of Si photonics with emphasis on the perspectives of Si nanoscale materials. Many of the results and properties can be simulated and understood based on theoretical studies. However, some of the key questions like the light-emitting mechanism are subjects of intense debates despite a remarkable progress in the recent years. Even more complex and important is to move the known experimental observations towards practical applications. The demonstrated devices and approaches are often too complex and/or have too low efficiency. However, the challenge to combine optical and electrical functions on a chip is very strong, and we expect more research activity in the field of Si nanophotonics in the future.

Critical micelle concentration (CMC) of two anionic surfactants in methanol was estimated using conductometry, viscometry and pyrene fluorescence spectroscopy methods. The surfactants used, were sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol-OT, AOT) and sodium dodecyl sulfate (SDS) dispersed in pure methanol. The CMC determination was evaluated in room temperature. The results have shown nearly similar concentrations. (C) 2012 Elsevier B.V. All rights reserved. Chemical Physics Letters

The synthesis, photophysical characterization and energy-transfer features of a series of hybrid truxene derivatives peripherally decorated with inorganic Os-containing polypyridine units and organic Bodipy dyes are reported. The photoactive terminal units are coupled to the central truxene scaffold by rigid ethynyl linkers in a star-shaped arrangement. The absorption range widely covers the UV-Vis spectrum and the Os (MLCT)-M-3 or the Bodipy triplet act as final collectors of the absorbed energy.

The excited state deactivation pathways of push–pull distyryl furan and benzofuran derivatives in several organic solvents were investigated in detail by using time-resolved transient absorption and fluorescence spectroscopies, with nano- and femto-second time resolution. Solvent polarity was found to play a key role in determining the efficiencies of fluorescence, intersystem crossing and internal conversion. The triplet yield gradually decreased, while the internal conversion increased upon increasing the solvent dielectric constant. However the fluorescence showed a different solvent polarity effect in the low and high solvent polarity region, with a reversal of the trend of fluorescence properties (quantum yield and lifetime). This fact points to an emitting state of a different nature (smaller and larger dipole moments) in the two cases, as also suggested by the huge fluorosolvatochromism. In fact the ultrafast spectroscopic investigation evidenced the presence of two transients characterized by peculiar spectral shapes assigned to a locally excited (LE) and a charge transfer (CT) state. In the more polar solvents the CT state was the longer lived, fluorescent one and an intramolecular charge transfer process was found to be operative and to become faster (up to B200–250 fs) in the higher polarity media. On the contrary, distyrylfuran, which exhibits the same molecular skeleton without the push–pull character showed a similar excited state dynamics in solvents of different polarities.