Pyrene, a Test Case for Deep-Ultraviolet Molecular Photophysics

We determined the complete relaxation dynamics of pyrene in ethanol from the second bright state, employing experimental and theoretical broadband heterodyne detected transient grating and two-dimensional photon echo (2DPE) spectroscopy, using pulses with duration of 6 fs and covering a spectral range spanning from 250 to 300 nm. Multiple lifetimes are assigned to conical intersections through a cascade of electronic states, eventually leading to a rapid population of the lowest long-living excited state and subsequent slow vibrational cooling. The lineshapes in the 2DPE spectra indicate that the efficiency of the population transfer depends on the kinetic energy deposited into modes required to reach a sloped conical intersection, which mediates the decay to the lowest electronic state. The presented experimental–theoretical protocol paves the way for studies on deep-ultraviolet-absorbing biochromophores ubiquitous in genomic and proteic systems

Thermessaite-(NH4), (NH4)2AlF3(SO4), a new fumarole mineral from la Fossa crater at Vulcano, Aeolian Islands, Italy

Thermessaite-(NH4), ideally (NH4)2AlF3(SO4), is a new mineral found as a medium- to high-temperature (about 250-300°C) fumarole encrustation at the rim of La Fossa crater, Vulcano, Aeolian Islands, Italy. The mineral deposited as aggregates of micrometer-sized sharp prismatic crystals on the surface of a pyroclastic breccia in association with thermessaite, sulfur, arcanite, mascagnite, and intermediate members of the arcanite-mascagnite series. The new mineral is colorless to white, transparent, non-fluorescent, has a vitreous luster, and a white streak. The calculated density is 2.185 g/cm3. Thermessaite-(NH4) is orthorhombic, space group Pbcn, with a = 11.3005(3) Å, b = 8.6125(3) Å, c = 6.8501(2) Å, V = 666.69(4) Å3, Z = 4. The eight strongest reflections in the X-ray powder-diffraction data [d in Å (I) (hkl)] are: 5.65 (100) (200), 4.84 (89) (111), 6.85 (74) (110), 3.06 (56) (112), 3.06 (53) (221), 3.08 (47) (311), 2.68 (28) (022), 2.78 (26) (130). The average chemical composition, determined by quantitative SEM-EDS (N by difference), is (wt%): K2O 3.38, Al2O325.35, SO336.58, F 26.12, (NH4)2O 22.47, O = F -11.00, total 102.90. The empirical chemical formula, calculated on the basis of 7 anions pfu, is [(NH4)1.85K0.15]Σ2.00Al106F2.94-S0.98O3.06. The crystal structure, determined from single-crystal X-ray diffraction data [R(F) = 0.0367], is characterized by corner-sharing AlF4O2octahedra which form [001] octahedral chains by sharing two trans fluoride atoms [Al-F2 = 1.8394(6) Å]. Non-bridging Al-F1 distances are shorter [1.756(1) Å]. The two trans oxygen atoms [Al-O = 1.920(2) Å] are from SO4tetrahedra. NH4+ions occur in layers parallel to (100) which alternate regularly with (100) layers containing ribbons of corner-sharing AlF4O2octahedra and associated SO4 groups. The NH4+ions are surrounded by five oxygen atoms and by four fluorine atoms. The mineral is named as the (NH4)-analogue of thermessaite, K2AlF3(SO4), and corresponds to an anthropogenic phase found in the burning Anna I coal dump of the Anna mine, Aachen, Germany. Both mineral and mineral name have been approved by the IMA-CNMNC commission (IMA 2011-077)

The “sant’angelo in criptis” cave church in santeramo in colle (Apulia, south italy): A multidisciplinary study for the evaluation of conservation state and stability assessment

Sant’Angelo in Criptis (Santeramo in Puglia, South Italy) is a karst cave located in the Alta Murgia National Park (aspiring geopark), presently degraded, but with signs of intense past visiting activity for worship, as testified by the beautiful wall paintings and the large number of inscriptions and engravings on the cave walls. With the aim to permit the desirable restoration and the following fruition of this ancient geo-cultural heritage, a multidisciplinary investigation of the cave was carried out in this study. The 3D cave model permitted a detailed map of the area and highlighted that the cave vault, although very regular, somewhere presents chimneys that develop upwards, indicating areas where the rock thickness is now very small. The stability analysis indicates that presently, the cave does not show remarkable signs of instability, but block failures, toppling and roof collapse are possible. Archaeometry investigations confirmed the past importance of this holy site, as testified by the overlapping in the paintings of three different pictorial cycles and the use of precious pigments, thus confirming the necessity of preservation through a conservation management strategy for a full future fruition of the cave

The effect of spatial variables on the economic and environmental performance of bioenergy production chains

The aim of this paper is to understand the impacts of spatial variables on the performance of bioenergy production chains (BPCs). Even though the strong debates continue on the use of first generation biomass for bioenergy production, many countries continue to utilize it as an alternative energy source. Several studies have been carried out on biomass transformation efficiency, on environmental impacts of using crop in biofuel production, and on its negative effects on increasing food prices. However, less attention has been paid to the role played by the spatial variables on the performance measures of BPCs. In this paper, we analyse how three spatial variables, i.e. cultivation area size, land dispersion, and accessibility to cultivation areas, can affect the performance of energy-balanced BPC, which produces its own electric and thermal energy demand. The chain is represented as a network of processes, where all inputs and outputs are geographically referred and analysed in a theoretical case example. We propose an enterprise input–output (EIO) model, which can be used as an accounting tool to compute the main materials and energy flows-related costs and as a planning tool to evaluate the chain performance in different scenarios. Finally, the proposed model is applied to an actual case study, to investigate the opportunity to establish a sunflower-based BPC in Apulia region (Italy) and to assess its performance. Results show that higher land dispersion degree and less area accessibility levels reduce the economic and environmental performance of the BPCs. The construction of the energy-balanced chain reduces the negative environmental impacts caused by fossil energy use in the processes of the BPC. Managerial implications can also be obtained from actual case study about the biodiesel plant location decisions

Experimental validation of a subject-specific finite element model of lumbar spine segment using digital image correlation

Pathologies such as cancer metastasis and osteoporosis strongly affect the mechanical properties of the vertebral bone and increase the risk of fragility fractures. The prediction of the fracture risk with a patient-specific model, directly generated from the diagnostic images of the patient, could help the clinician in the choice of the correct therapy to follow. But before such models can be used to support any clinical decision, their credibility must be demonstrated through verification, validation, and uncertainty quantification. In this study we describe a procedure for the generation of such patient-specific finite element models and present a first validation of the kinematics of the spine segment. Quantitative computed tomography images of a cadaveric lumbar spine segment presenting vertebral metastatic lesions were used to generate the model. The applied boundary conditions replicated a specific experimental test where the spine segment was loaded in compression-flexion. Model predictions in terms of vertebral surface displacements were compared against the full-field experimental displacements measured with Digital Image Correlation. A good agreement was obtained from the local comparison between experimental data and simulation results (R2 > 0.9 and RMSE% <8%). In conclusion, this work demonstrates the possibility to apply the developed modelling pipeline to predict the displacement field of human spine segment under physiological loading conditions, which is a first fundamental step in the credibility assessment of these clinical decision-support technology

Spectroscopic fingerprints of DNA/RNA pyrimidine nucleobases in third-order nonlinear electronic spectra

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

Coupled Electronic and Nuclear Motions during Azobenzene Photoisomerization Monitored by Ultrafast Electron Diffraction

Ultrafast electron diffraction is a powerful technique that can resolve molecular structures with femtosecond and angstrom resolutions. We demonstrate theoretically how it can be used to monitor conical intersection dynamics in molecules. Specific contributions to the signal are identified which vanish in the absence of vibronic coherence and offer a direct window into conical intersection paths. A special focus is on hybrid scattering from nuclei and electrons, a process that is unique to electron (rather than X-ray) diffraction and monitors the strongly coupled nuclear and electronic motions in the vicinity of conical intersections. An application is made to the cis to trans isomerization of azobenzene, computed with exact quantum dynamics wavepacket propagation in a reactive two-dimensional nuclear space

Parameterization of a linear vibronic coupling model with multiconfigurational electronic structure methods to study the quantum dynamics of photoexcited pyrene

With this work, we present a protocol for the parameterization of a Linear Vibronic Coupling (LVC) Hamiltonian for quantum dynamics using highly accurate multiconfigurational electronic structure methods such as RASPT2/RASSCF, combined with a maximum-overlap diabatization technique. Our approach is fully portable and can be applied to many medium-size rigid molecules whose excited state dynamics requires a quantum description. We present our model and discuss the details of the electronic structure calculations needed for the parameterization, analyzing critical situations that could arise in the case of strongly interacting excited states. The protocol was applied to the simulation of the excited state dynamics of the pyrene molecule, starting from either the first or the second bright state (S2 or S5). The LVC model was benchmarked against state-of-the-art quantum mechanical calculations with optimizations and energy scans and turned out to be very accurate. The dynamics simulations, performed including all active normal coordinates with the multilayer multiconfigurational time-dependent Hartree method, show good agreement with the available experimental data, endorsing prediction of the excited state mechanism, especially for S5, whose ultrafast deactivation mechanism was not yet clearly understood

Computing the absorption and emission spectra of 5-methylcytidine in different solvents: a test-case for different solvation models

International audience; The optical spectra of 5-methylcytidine in three different solvents (tetrahydrofuran, acetonitrile, and water) is measured, showing that both the absorption and the emission maximum in water are significantly blue-shifted (0.08 eV). The absorption spectra are simulated based on CAM-B3LYP/TD-DFT calculations but including solvent effects with three different approaches: (i) a hybrid implicit/explicit full quantum mechanical approach, (ii) a mixed QM/MM static approach, and (iii) a QM/MM method exploiting the structures issuing from molecular dynamics classical simulations. Ab-initio Molecular dynamics simulations based on CAM-B3LYP functionals have also been performed. The adopted approaches all reproduce the main features of the experimental spectra, giving insights on the chemical−physical effects responsible for the solvent shifts in the spectra of 5-methylcytidine and providing the basis for discussing advantages and limitations of the adopted solvation models