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In this study, we explore the behavior of endohedral fullerenes and examine how different doping species influence the ultrafast photoinduced electronic dynamics. We analyzed a reference fullerene (C60) and two endohedral fullerenes with Cl–and Mg atoms inside the cage using electronic dynamics calculations. By applying circularly polarized light, we observed the transfer of angular momentum from the light to the electron density in these systems. The optical properties and specific excitations were determined through quantum chemical calculations, which formed the basis of our analysis. In the C60reference system, excitation led to a significant rotation of the electron density and the formation of a large rotating dipole. For the Mg@C60 system, the electron density changes were mostly localized around the Mg atom, resulting in a smaller induced dipole but more localized excitations. In the Cl–@C60system, minimal angular momentum transfer was observed with an isotropic distribution of charges due to the charge-transfer nature of the excitations. The distinct behaviors observed in these systems highlight the diverse phenomena that can arise and represent a significant step toward developing novel molecular devices.

High-Harmonic Generation (HHG) spectra of randomly aligned bromoform (CHBr3) molecules have been experimentally measured and theoretically simulated at various laser pulse intensities. From the experiments, we obtained a significant number of harmonics that goes beyond the cutoff limit predicted by the three-step model (3SM) with ionization from HOMO. To interpret the experiment, we resorted to real-time time-dependent configuration interaction with single excitations. We found that electronic bound states provide an appreciable contribution to the harmonics. More in detail, we analyzed the electron dynamics by decomposing the HHG signal in terms of single molecular-orbital contributions, to explain the appearance of harmonics around 20–30 eV beyond the expected cutoff due to HOMO. HHG spectra can be therefore explained by considering the contribution at high energy of HOMO–6 and HOMO–9, thus indicating a complex multiple-orbital strong-field dynamics. However, even though the presence of the bromoform cation should be not enough to produce such a signal, we could not exclude a priori that the origin of harmonics in the H29–H45 to be due to the cation, which has more energetic ionization channels.

Plasmonic-driven photocatalysis may lead to reaction selectivity that cannot be otherwise achieved. A fundamental role is played by hot carriers, i.e., electrons and holes generated upon plasmonic decay within the metal nanostructure interacting with molecular species. Understanding the elusive microscopic mechanism behind such selectivity is a key step in the rational design of hot-carrier reactions. To accomplish that, we present state-of-the-art multiscale simulations, going beyond density functional theory, of hot-carrier injections for the rate-determining step of a photocatalytic reaction. We focus on carbon dioxide reduction, for which it was experimentally shown that the presence of a rhodium nanocube under illumination leads to the selective production of methane against carbon monoxide. We show that selectivity is due to a (predominantly) direct hole injection from rhodium to the reaction intermediate CHO. Unexpectedly, such an injection does not promote the selective reaction path by favoring proper bond breaking but rather by promoting bonding of the proper molecular fragment to the surface.

The article discusses the concept of immersion and the interconnectedness between living beings and their environment. It challenges traditional models of understanding this relationship and emphasizes the mutual influence between organisms and their surroundings. The text explores the discovery of photosynthesis by Jan Ingenhousz and the role of plants in transforming the atmosphere. It also delves into the concept of the atmosphere as a metaphysical space of unity and the importance of breath in sustaining life. The given text provides references and citations for further research on topics such as the evolution of oxygen, the concept of atmosphere, and the history of photosynthesis research. Additionally, it mentions a book by Emanuele Coccia that explores the relationship between domestic space and happiness. [Extracted from the article]

This article explores an archaeological experiment that took place in the basements beneath the La Défense slab in Paris. The experiment focused on the future of our world and introduced two entities, Petrophytis and Petrogaia, that represent a combination of mineral, plant, and technological elements. The experiment challenges the concept of evolution and encourages thinking about life in terms of metamorphosis and transformation. The article also discusses a film called "The Dispute" that explores ecological beings, evolutionary theories, and the right to forget. It mentions the production of the film and the setting of La Défense, as well as a forbidden underground area in La Défense that is home to graffiti artists and a homeless population. The film and the underground area serve as immersive zones that challenge our relationship to space and time. [Extracted from the article]

In an interview with Log magazine, philosophy professor Emanuele Coccia discusses his interest in architecture and the city. He emphasizes the importance of the home in architectural theory and explores the relationship between architecture and digital space. Coccia criticizes the lack of vision among architects and calls for a new architectural renaissance. He also highlights the role of architecture in maintaining our relationship with nature and other species. The interview covers various topics including art, museums, and the democratization of curating in the digital age. Coccia argues for a more coherent and contemporary approach to urban planning, emphasizing the need to think from a planetary perspective. [Extracted from the article]

In this work, we decompose the high-harmonic generation (HHG) signal of aligned gas-phase uracil into single molecular-orbital (MO) contributions. We compute HHG spectra for a pulse linearly polarized perpendicular to the molecular plane, with an intensity of 0.6 and 0.85 × 1014W/cm2and a wavelength of 800 nm. We use the real-time time-dependent Configuration Interaction with singles method, coupled to a Gaussian-based representation of the time-dependent wavefunction. The strong-field dynamics is affected by the energy of the ionization/recombination channels and by the coupling between the orbital symmetry and laser polarization. In the configuration studied here, we expect that π-type MOs favorably couple with the incoming pulse and play a substantial role in generating the HHG spectrum. Indeed, we show that HOMO, HOMO – 1, and HOMO – 4, which all are π-like, determine the intensity of harmonic peaks at different energies, while HOMO – 2 and HOMO – 3 provide a smaller contribution. It is worth mentioning that HOMO – 4 produces a stronger signal than that from HOMO – 1, even though the corresponding ionization energy, in an one-electron picture, is around 2.5 eV larger and more than 4 eV larger than the HOMO one.

BackgroundKBG syndrome is caused by haploinsufficiency of ANKRD11and is characterised by macrodontia of upper central incisors, distinctive facial features, short stature, skeletal anomalies, developmental delay, brain malformations and seizures. The central nervous system (CNS) and skeletal features remain poorly defined.MethodsCNS and/or skeletal imaging were collected from molecularly confirmed individuals with KBG syndrome through an international network. We evaluated the original imaging and compared our results with data in the literature.ResultsWe identified 53 individuals, 44 with CNS and 40 with skeletal imaging. Common CNS findings included incomplete hippocampal inversion and posterior fossa malformations; these were significantly more common than previously reported (63.4% and 65.9% vs 1.1% and 24.7%, respectively). Additional features included patulous internal auditory canal, never described before in KBG syndrome, and the recurrence of ventriculomegaly, encephalic cysts, empty sella and low-lying conus medullaris. We found no correlation between these structural anomalies and epilepsy or intellectual disability. Prevalent skeletal findings comprised abnormalities of the spine including scoliosis, coccygeal anomalies and cervical ribs. Hand X-rays revealed frequent abnormalities of carpal bone morphology and maturation, including a greater delay in ossification compared with metacarpal/phalanx bones.ConclusionThis cohort enabled us to describe the prevalence of very heterogeneous neuroradiological and skeletal anomalies in KBG syndrome. Knowledge of the spectrum of such anomalies will aid diagnostic accuracy, improve patient care and provide a reference for future research on the effects of ANKRD11variants in skeletal and brain development.

The article reviews the exhibition "Grand Atlas de la désorientation" by Tatiana Trouvé at the Centre Pompidou in Europe from June 8 to August 22, 2022 curated by Jean-Pierre Criqui and assisted by Annalise Rimmaudo.

The article discusses exhibition called "Diversion," Asad Raza rerouted the Main River to flow through Kunsthalle Portikus in Frankfurt.

The article focuses on "After UUmwelt" exhibition featuring work of artist Pierre Huyghe at Grande Halle of the LUMA Foundation in Arles, France through October 31, 2021.

The article features artist Philippe Parreno and his artworks. Also cited are the anthropomorphic psychism in Parreno's art, his animation work "No Ghost Just a Shell," the subjectivity, narcissism and commodification in Parreno's art, and his other works like "Marilyn" in 2012, "The Writer" in 2007, and "Anywhen" in 2017.

The article focuses on politics which is self-portrait in manner of Kabbalistic belief in contraction of God's light and mentions humanity which will begin experiment with global monasticism. Topics discussed include God related to world not much as political leader in Christian sphere, SARS-CoV2 which has been radicalization of ecological thinking, and domestic revolution to think house no longer as space of property.

The article examines the representation of metamorphosis and alchemy in the art of Bianca Bondi. Topics covered include how the vitrine, the technical apparatus that Bondi's art makes use of, is the result of the fusion between art and reality, the influence of Bondi's animist faith on her art, and how her installations which make use of the vitrines and plastic bags produce a diversion of certain elements and objects from the history of the world.

The structures of three negatively charged forms (anionic keto-1 and enol-1 and dianionic enol-2) of oxyluciferin (OxyLuc), which are the most probable emitters responsible for the firefly bioluminescence, have been fully relaxed at the variational Monte Carlo (VMC) level. Absorption energies of the S1← S0vertical transition have been computed using different levels of theory, such as TDDFT, CC2, and many-body Green’s function theory (MBGFT). The use of MBGFT, by means of the Bethe–Salpeter (BS) formalism, on VMC structures provides results in excellent agreement with the value (2.26(8) eV) obtained by action spectroscopy experiments for the keto-1 form (2.32 eV). To unravel the role of the quality of the optimized ground-state geometry, BS excitation energies have also been computed on CASSCF geometries, inducing a non-negligible blue shift (0.08 and 0.07 eV for keto-1 and enol-1 forms, respectively) with respect to the VMC ones. Structural effects have been analyzed in terms of over- or undercorrelation along the conjugated bonds of OxyLuc by using different methods for the ground-state optimization. The relative stability of the S1state for the keto-1 and enol-1 forms depends on the method chosen for the excited-state calculation, thus representing a fundamental caveat for any theoretical study on these systems. Finally, Kohn–Sham HOMO and LUMO orbitals of enol-2 are (nearly) bound only when the dianion is embedded into a solvent (water and toluene in the present work); excited-state calculations are therefore meaningful only in the presence of a dielectric medium which localizes the electronic density. The combination of VMC for the ground-state geometry and BS formalism for the absorption spectra clearly outperforms standard TDDFT and quantum chemistry approaches.

A clear understanding of the mechanisms that control the electron dynamics in a strong laser field is still a challenge that requires interpretation by advanced theory. Development of accurate theoretical and computational methods, able to provide a precise treatment of the fundamental processes generated in the strong field regime, is therefore crucial. A central aspect is the choice of the basis for the wave function expansion. Accuracy in describing multiphoton processes is strictly related to the intrinsic properties of the basis, such as numerical convergence, computational cost, and representation of the continuum. By explicitly solving the 1D and 3D time-dependent Schrödinger equation for H2+in the presence of an intense electric field, we explore the numerical performance of using a real-space grid, a B-spline basis, and a Gaussian basis (improved by optimal Gaussian functions for the continuum). We analyze the performance of the three bases for high-harmonic generation and above-threshold ionization for H2+. In particular, for high-harmonic generation, the capability of the basis to reproduce the two-center interference and the hyper-Raman phenomena is investigated.

Abstract:This interview with Italian philosopher Emanuele Coccia revisits key problems of his thought, with particular attention to the imagination, Averroism, sensation, political theology, and anthropology. The occasion for this conversation was Coccia’s recent English translation of Sensible Life (2016), a book that decisively expands his notion of mediality of the sensible as to reimage the concept of life. The interview also deals with a wide range of topics, such as the arrangement of the modern university as well as Coccia’s most recent work on modern publicity and advertisement and the immersion of the lives of plants.

Electron correlation plays a crucial role in the energetics of reactions catalyzed by transition metal complexes, such as water splitting. In the present work we exploit the performance of various methods to describe the thermodynamics of a simple but representative model of water splitting reaction, based on a single cobalt ion as catalyst. Density Functional Theory (DFT) calculations show a significant dependence on the adopted functional, and not negligible differences with respect to CCSD(T) findings are found along the reaction cycle. We performed quantum Monte Carlo calculations using an unrestricted single Slater determinant wave function multiplied by a Jastrow factor using both DFT and fully optimized orbitals. Variational and Lattice Regularized Diffusion Monte Carlo results are in overall agreement with the CCSD(T) free-energy profile, even though differences in the description of the thermodynamics of the reaction cycle are found. NEVPT2 calculations reveal that the role of the static correlation of the different reaction steps is not large, and it is limited to only a few intermediate structures. Finally, the free-energy difference of the overall water splitting reaction computed at the quantum Monte Carlo level shows an excellent match with the experimental value of 4.92 eV, underlining the capability of these techniques to properly describe the dynamical correlation of such reactions.

Disjoint non-Kekulé molecules are diradicals that present two independent radical centers and can violate Hund’s rule, according to which the ground state should have triplet spin symmetry. The prototype of this class of systems is the tetramethyleneethane (TME) molecule for which indeed ion photoelectron spectroscopy (IPS) experiments revealed the singlet 1A state to be more stable than the triplet 3Bu. In this work we investigate the potential energy curves of the two spin states of TME and of the two anionic states of TME–(2A and 2B1) as a function of the torsion of the central dihedral angle, with quantum Monte Carlo methods and a Jastrow Antisymmetrized Geminal Power wave function. Through ab initiogeometrical optimizations we study the possible structural interconversions between the states, finding results which are in full agreement with the IPS experimental data.

The penta-2,4-dieniminium cation (PSB3) displays similar ground state and first excited state potential energy features as those of the retinal protonated Schiff base (RPSB) chromophore in rhodopsin. Recently, PSB3 has been used to benchmark several electronic structure methods, including highly correlated multireference wave function approaches, highlighting the necessity to accurately describe the electronic correlation in order to obtain reliable properties even along the ground state (thermal) isomerization paths. In this work, we apply two quantum Monte Carlo approaches, the variational Monte Carlo and the lattice regularized diffusion Monte Carlo, to study the energetics and electronic properties of PSB3 along representative minimum energy paths and scans related to its thermal cis–transisomerization. Quantum Monte Carlo is used in combination with the Jastrow antisymmetrized geminal power ansatz, which guarantees an accurate and balanced description of the static electronic correlation thanks to the multiconfigurational nature of the antisymmetrized geminal power term, and of the dynamical correlation, due to the presence of the Jastrow factor explicitly depending on electron–electron distances. Along the two ground state isomerization minimum energy paths of PSB3, CASSCF calculations yield wave functions having either charge transfer or diradical character in proximity of the two transition state configurations. Here, we observe that at the quantum Monte Carlo level of theory, only the transition state with charge transfer character can be located. The conical intersection, which becomes highly sloped, is observed only if the path connecting the two original CASSCF transition states is extended beyond the diradical one, namely by increasing the bond-length-alternation (BLA). These findings are in good agreement with the results obtained by MRCISD+Q calculations, and they demonstrate the importance of having an accurate description of the static and dynamical correlation when studying isomerization and transition states of conjugated systems.

Diradical molecules are essential species involved in many organic and inorganic chemical reactions. The computational study of their electronic structure is often challenging, because a reliable description of the correlation, and in particular of the static one, requires multireference techniques. The Jastrow correlated antisymmetrized geminal power (JAGP) is a compact and efficient wave function ansatz, based on the valence-bond representation, which can be used within quantum Monte Carlo (QMC) approaches. The AGP part can be rewritten in terms of molecular orbitals, obtaining a multideterminant expansion with zero-seniority number. In the present work we demonstrate the capability of the JAGP ansatz to correctly describe the electronic structure of two diradical prototypes: the orthogonally twisted ethylene, C2H4, and the methylene, CH2, representing respectively a homosymmetric and heterosymmetric system. In the orthogonally twisted ethylene, we find a degeneracy of π and π* molecular orbitals, as correctly predicted by multireference procedures, and our best estimates of the twisting barrier, using respectively the variational Monte Carlo (VMC) and the lattice regularized diffusion Monte Carlo (LRDMC) methods, are 71.9(1) and 70.2(2) kcal/mol, in very good agreement with the high-level MR-CISD+Q value, 69.2 kcal/mol. In the methylene we estimate an adiabatic triplet–singlet (X̃3B1–ã1A1) energy gap of 8.32(7) and 8.64(6) kcal/mol, using respectively VMC and LRDMC, consistently with the experimental-derived finding for Te, 9.363 kcal/mol. On the other hand, we show that the simple ansatz of a Jastrow correlated single determinant (JSD) wave function is unable to provide an accurate description of the electronic structure in these diradical molecules, both at variational level (VMC torsional barrier of C2H4of 99.3(2) kcal/mol, triplet–singlet energy gap of CH2of 13.45(10) kcal/mol) and, more remarkably, in the fixed-nodes projection schemes (LRDMC torsional barrier of 97.5(2) kcal/mol, triplet–singlet energy gap of 13.36(8) kcal/mol) showing that a poor description of the static correlation yields an inaccurate nodal surface. The suitability of JAGP to correctly describe diradicals with a computational cost comparable with that of a JSD calculation, in combination with a favorable scalability of QMC algorithms with the system size, opens new perspectives in the ab initio study of large diradical systems, like the transition states in cycloaddition reactions and the thermal isomerization of biological chromophores.

In this letter, we report the singlet ground state structure of the full carotenoid peridinin by means of variational Monte Carlo (VMC) calculations. The VMC relaxed geometry has an average bond length alternation of 0.1165(10) Å, larger than the values obtained by DFT (PBE, B3LYP, and CAM-B3LYP) and shorter than that calculated at the Hartree–Fock (HF) level. TDDFT and EOM-CCSD calculations on a reduced peridinin model confirm the HOMO–LUMO major contribution of the Bu+-like (S2) bright excited state. Many Body Green’s Function Theory (MBGFT) calculations of the vertical excitation energy of the Bu+-like state for the VMC structure (VMC/MBGFT) provide an excitation energy of 2.62 eV, in agreement with experimental results in n-hexane (2.72 eV). The dependence of the excitation energy on the bond length alternation in the MBGFT and TDDFT calculations with different functionals is discussed.

The accurate determination of the geometrical details of the dark state of 11-cisretinal in rhodopsin represents a fundamental step for the rationalization of the protein role in the optical spectral tuning in the vision mechanism. We have calculated geometries of the full retinal protonated Schiff base chromophore in the gas phase and in the protein environment using the correlated variational Monte Carlo method. The bond length alternation of the conjugated carbon chain of the chromophore in the gas phase shows a significant reduction when moving from the β-ionone ring to the nitrogen, whereas, as expected, the protein environment reduces the electronic conjugation. The proposed dark state structure is fully compatible with solid-state NMR data reported by Carravetta et al. [J. Am. Chem. Soc. 2004, 126, 3948–3953]. TDDFT/B3LYP calculations on such geometries show a blue opsin shift of 0.28 and 0.24 eV induced by the protein for S1and S2states, consistently with literature spectroscopic data. The effect of the geometrical distortion alone is a red shift of 0.21 and 0.16 eV with respect to the optimized gas phase chromophore. Our results open new perspectives for the study of the properties of chromophores in their biological environment using correlated methods.

We used Quantum Monte Carlo (QMC) methods to study the polarizability and the quadrupole moment of the ethyne molecule using the Jastrow-Antisymmetrised Geminal Power (JAGP) wave function, a compact and strongly correlated variational ansatz. The compactness of the functional form and the full optimization of all its variational parameters, including linear and exponential coefficients in atomic orbitals, allow us to observe a fast convergence of the electrical properties with the size of the atomic and Jastrow basis sets. Both variational results on isotropic polarizability and quadrupole moment based on Gaussian type and Slater type basis sets are very close to the Lattice Regularized Diffusion Monte Carlo values and in very good agreement with experimental data and with other quantum chemistry calculations. We also study the electronic density along the CC and C–H bonds by introducing a generalization for molecular systems of the small-variance improved estimator of the electronic density proposed by Assaraf et al. (Assaraf, R.; Caffarel, M.; Scemama, A. Phys. Rev. E, 2007, 75, 035701).

Starting from the analysis of Bernard’s of Clairvaux work De praecepto et dispensatione,the article focuses on the ancient and medieval regulae vivendiin order to demonstrate that they represent a specific form of normativity, absolutely different from the classical roman jusand the medieval canon law. I analyze the peculiar way in which Bernard tried to describe the particular normative logic of the Rule of Benedict from the point of view of a western legal history of longue durée.In comparison with the civil law and the ecclesiastical legislation, a “rule of life” (regula vitae) is a special form of law which extends to the complete life of the individual, not a single moment. The juridical institution of the vow has an important place in this special normative logic.

Lurbinectedin is responsible for DNA recognition and binding, producing double-strand DNA (dsDNA) breaks thus resulting in apoptosis. Sensitivity to lurbinectedin is linked to the nucleotide excision repair (NER) system. Furthermore, irinotecan, a topoisomerase I inhibitor, provokes dsDNA breaks that could be reinforced abrogating the NER system using lurbinectedin. BRCA-mutated patients, already treated with platinum-derived drugs, who suffered DNA damage, cannot repair the breaks due to lurbinectedin interaction, whereas irinotecan provokes a dsDNA break that promotes synthetic lethality. This article describes an exceptional response to lurbinectedin alone followed by the association with irinotecan in a BRCA-mutated platinum-resistant ovarian cancer patient. A 44-year-old BRCA1-mutated ovarian cancer patient was treated in sixth line with lurbinectedin and irinotecan with a time to further progression (TTFP) equal to 8 months. In our case, the association with irinotecan overcame the resistance to lurbinectedin alone. In conclusion, lurbinectedin and irinotecan demonstrated a promising response in platinum-resistant patients. However, further studies should be conducted to validate our findings and future trials will be important to further define the clinical utility of lurbinectedin.