Capturing electron-driven chiral dynamics in UV-excited molecules.

Chiral molecules, used in applications such as enantioselective photocatalysis1, circularly polarized light detection2 and emission3 and molecular switches4,5, exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale6 and thereby control reactivity7-9. Electron currents in photoexcited chiral molecules have indeed been predicted to enable enantiosensitive molecular orientation10, but electron-driven chiral dynamics in neutral molecules have not yet been demonstrated owing to the lack of ultrashort, non-ionizing and perturbative light pulses. Here we use time-resolved photoelectron circular dichroism (TR-PECD)11-15 with an unprecedented temporal resolution of 2.9 fs to map the coherent electronic motion initiated by ultraviolet (UV) excitation of neutral chiral molecules. We find that electronic beatings between Rydberg states lead to periodic modulations of the chiroptical response on the few-femtosecond timescale, showing a sign inversion in less than 10 fs. Calculations validate this and also confirm that the combination of the photoinduced chiral current with a circularly polarized probe pulse realizes an enantioselective filter of molecular orientations following photoionization. We anticipate that our approach will enable further investigations of ultrafast electron dynamics in chiral systems and reveal a route towards enantiosensitive charge-directed reactivity.

Modifications of Tanabe-Sugano d6 Diagram Induced by Radical Ligand Field: Ab Initio Inspection of a Fe(II)-Verdazyl Molecular Complex.

Quantum entanglement between the spin states of a metal center and radical ligands is suggested in an iron(II) [Fe(dipyvd)2]2+ compound (dipyvd = 1-isopropyl-3,5-dipyridil-6-oxoverdazyl). Wave function ab initio (Difference Dedicated Configuration Interaction, DDCI) inspections were carried out to stress the versatility of local spin states. We named this phenomenon excited state spinmerism, in reference to our previous work (see Roseiro et al., ChemPhysChem 2022, e202200478) where we introduced the concept of spinmerism as an extension of mesomerism to spin degrees of freedom. The construction of localized molecular orbitals allows for a reading of the wave functions and projections onto the local spin states. The low-energy spectrum is well-depicted by a Heisenberg picture. A 60 cm-1 ferromagnetic interaction is calculated between the radical ligands with the Stotal = 0 and 1 states largely dominated by a local low-spin SFe = 0. In contrast, the higher-lying Stotal = 2 states are superpositions of the local SFe = 1 (17%, 62%) and SFe = 2 (72%, 21%) spin states. Such mixing extends the traditional picture of a high-field d6 Tanabe-Sugano diagram. Even in the absence of spin-orbit coupling, the avoided crossing between different local spin states is triggered by the field generated by radical ligands. This puzzling scenario emerges from versatile local spin states in compounds which extend the traditional views in molecular magnetism.

Combining Open-Shell Verdazyl Environment and Co(II) Spin-Crossover: Spinmerism in Cobalt Oxoverdazyl Compound.

The spin states of a Co(II) oxoverdazyl compound are investigated by means of wavefunction-based calculations. Within a ca. 233 K energy window, the ground state and excited states display a structure-sensitive admixture of low-spin SM =1/2 in a dominant high-spin SM =3/2 Co(II) ion as indicated by the localized molecular orbitals. The puzzling spin zoology that results from the coupling between open-shell radical ligands and a spin-crossover metal ion gives rise to this unusual scenario, which extends the views in molecular magnetism. In agreement with experimental observation, the low-energy spectroscopy is very sensitive to deformations of the coordination sphere, and a growing admixture of Co(II) low-spin is evidenced from the calculations. In analogy with mesomerism that accounts for charge delocalization, entanglement combines different local spin states to generate a given total spin multiplicity, a spinmerism phenomenon.

Difficulty of the evaluation of the barrier height of an open-shell transition state between closed shell minima: The case of small C4n rings.

C4n cyclacenes exhibit strong bond-alternation in their equilibrium geometry. In the two equivalent geometries, the system keeps an essentially closed-shell character. The two energy minima are separated by a transition state suppressing the bond-alternation, where the wave function is strongly diradical. This paper discusses the physical factors involved in this energy difference and possible evaluations of the barrier height. The barrier given as the energy difference between the restricted density functional theory (DFT)/B3LYP for the equilibrium and the broken symmetry DFT/B3LYP of the transition state is either negative or small, in contradiction with the most reliable Wave Function Theory calculations. The minimal (two electrons in two molecular orbitals) Complete Active Space self-consistent field (CASSCF) overestimates the barrier, and the subsequent second-order perturbation cancels it. Due to the collective character of the spin-polarization effect, it is necessary to perform a full π CASSCF + second-order perturbation to reach a reasonable value of the barrier, but this type of treatment cannot be applied to large molecules. DFT procedures treating on an equal foot the closed-shell and open-shell geometries have been explored, such as Mixed-Reference Spin-Flip Time-dependent-DFT and a new spin-decontamination proposal, namely, DFT-dressed configuration interaction, but the results still depend on the density functional. M06-2X without or with spin-decontamination gives the best agreement with the accurate wave function results.

Is fat taste associated with diet quality? A cross-sectional study conducted among Tunisian adults.

The Tunisian population has experienced a nutrition transition with an increase in the incidence of obesity. As obesity has been associated with a poor orosensory detection of fat. We hypothesized that poor fat detection could be a driver of poor diet quality. This study examined the association between linoleic acid (LA) detection and adherence to a healthy diet among adult participants. A total of 104 LA taster participants were recruited for this study. Dietary assessment was conducted using the 24 h dietary recall method. Diet quality was assessed by determining the Mediterranean diet (MD) score and Health diet indicator (HDI). The relationship between diet quality and log LA detection threshold was done using adjusted linear regression for age, sex, and daily energy intake (only in the fully adjusted model). The predictive margins model (interaction: anthropometric status x LA threshold) was used to assess the difference between non-obese and subjects with obesity adherence to MD across LA detection values. We have observed that the increase in the concentration of linoleic acid detection by 1 log(mmol/L) is associated with an increase of HDI score by 0.12-point [95% CI: 0.02-0.21] and a decrease of the MD score by -0.14-point [-0.25 to -0.03] in the partially adjusted model. However, only the MD score remained negatively associated with LA detection threshold in the fully adjusted model. The subjects with obesity adherence to the Mediterranean diet was lower than subjects with normal weight for LA concentration less than 0 log(mmol/L). The present study suggests that poor orosensory detection of dietary lipids might be a driver for worsening diet quality. Hence, These subjects might be at risk for obesity and, consequently, exposed cumulatively to the harmful effects of excess adiposity and an unhealthy diet.

Model protein excited states: MRCI calculations with large active spaces vs CC2 method.

Benchmarking calculations on excited states of models of phenylalanine protein chains are presented to assess the ability of alternative methods to the standard and most commonly used multiconfigurational wave function-based method, the complete active space self-consistent field (CASSCF), in recovering the non-dynamical correlation for systems that become not affordable by the CASSCF. The exploration of larger active spaces beyond the CASSCF limit is benchmarked through three strategies based on the reduction in the number of determinants: the restricted active space self-consistent field, the generalized active space self-consistent field (GASSCF), and the occupation-restricted multiple active space (ORMAS) schemes. The remaining dynamic correlation effects are then added by the complete active space second-order perturbation theory and by the multireference difference dedicated configuration interaction methods. In parallel, the approximate second-order coupled cluster (CC2), already proven to be successful for small building blocks of model proteins in one of our previous works [Ben Amor et al., J. Chem. Phys. 148, 184105 (2018)], is investigated to assess its performances for larger systems. Among the different alternative strategies to CASSCF, our results highlight the greatest efficiency of the GASSCF and ORMAS schemes in the systematic reduction of the configuration interaction expansion without loss of accuracy in both nature and excitation energies of both singlet ππ* and nπ* CO excited states with respect to the equivalent CASSCF calculations. Guidelines for an optimum applicability of this scheme to systems requiring active spaces beyond the complete active space limit are then proposed. Finally, the extension of the CC2 method to such large systems without loss of accuracy is demonstrated, highlighting the great potential of this method to treat accurately excited states, mainly single reference, of very large systems.

Origin of Ferromagnetism and Magnetic Anisotropy in a Family of Copper(II) Triangles.

Previously reported ferromagnetic triangles (NnBu4 )2 [Cu3 (µ3 -Cl)2 (µ-4-NO2 -pz)3 Cl3 ] (1), (PPN)2 [Cu3 (µ3 -Cl)2 (µ-pz)3 Cl3 ] (2), (bmim)2 [Cu3 (µ3 -Cl)2 (µ-pz)3 Cl3 ] (3) and newly reported (PPh4 )2 [Cu3 (µ3 -Cl)2 (µ-4-Ph-pz)3 Cl3 ] (4) were studied by magnetic susceptometry, electron paramagnetic resonance (EPR) spectroscopy and ab initio calculations to assess the origins of their ferromagnetism and of the magnetic anisotropy of their ground S=3/2 state (PPN+ =bis(triphenylphosphine)iminium, bmim+ =1-butyl-3-methylbenzimidazolium, pz- =pyrazolate). Ab initio studies revealed the d z 2 character of the magnetic orbitals of the compressed trigonal bipyramidal copper(II) ions. Ferromagnetic interactions were attributed to weak orbital overlap via the pyrazolate bridges. From the wavefunctions expansions, the ratios of the magnetic couplings were determined, which were indeterminate by magnetic susceptometry. Single-crystal EPR studies of 1 were carried out to extend the spin Hamiltonian with terms which induce zero-field splitting (zfs), namely dipolar interactions, anisotropic exchange and Dzyaloshinskii-Moriya interactions (DMI). The data were treated through both a giant-spin model and through a multispin exchange-coupled model. The latter indicated that ≈62 % of the zfs is due to anisotropic and ≈38 % due to dipolar interactions. The powder EPR data of all complexes were fitted to a simplified form of the multispin model and the anisotropic and dipolar contributions to the ground state zfs were estimated.

Spin polarization as an electronic cooperative effect.

Taking as an example the simple CH3 radical, this work demonstrates the cooperative character of the spin-polarization phenomenon of the closed-shell core in free radicals. Spin polarization of CH σ bonds is not additive here, as spin polarization of one bond enhances that of the next bond. This cooperativity is demonstrated by a series of configuration interaction calculations converging to the full valence limit and is rationalized by analytic developments. The same phenomenon is shown to take place in those diradicals where spin polarization plays a major role, as illustrated in square planar carbo-cyclobutadiene C12H4. The treatment of cooperativity represents a challenge for usual post-Hatree-Fock methods.

RASPT2 study of the valence excited states of an iron-porphyrin-carbonyl model complex.

Multireference wavefunction calculations of the singlet valence excited states of an iron-porphyrin-pyrazine-carbonyl complex up to the Soret band (about 3 eV) are presented. This complex is chosen to be a model for the active site of carboxyhemoglobin/carboxymyoglobin. The investigations are performed at the restricted active space second-order perturbation (RASPT2) level involving an extended active space on the porphyrin ligand in addition to the active orbitals needed for the description of the metal-ligand interactions. Metal-to-ligand-charge-transfer states d → π* and some metal-centered d → d transitions are found in the lowest part of the spectrum, below the first π → π* intraporphyrin transitions (Q band). Doubly excited states involving simultaneous intraporphyrin and metal-centered excitations are found in the vicinity of the second set of intraporphyrin transitions (the so-called Soret band). The effect of the extension of the active space on the porphyrin ligand beyond the Gouterman's orbitals set is investigated together with the effect of inclusion of the ionization potential electron affinity shift in the RASPT2 treatment. © 2019 Wiley Periodicals, Inc.

Ultrafast electronic relaxations from the S3 state of pyrene.

The ultrafast relaxation occurring in pyrene upon excitation at 4.68 eV was studied in a supersonic gas-jet fs pump-probe experiment. Mass spectrometry and velocity map imaging of photoelectrons produced by probing via multiphoton ionisation at 800 nm reveal that the initially prepared wave packet exhibits a fast relaxation (<80 fs), followed by a slower one of 200 fs. By comparing the propensity rules of photoionisation observed at one color with ab initio calculations, we tentatively assign these two timescales to a first internal conversion to the dark bB3g state followed by a second one to the long lived aB2u first excited state. Vertical excitation energies determined using ab initio Multi-State Complete Active Space 2nd order Perturbation Theory (MS-CASPT2), as well as oscillator strengths between several electronic states, are reported.

Theoretical determination of adsorption and ionisation energies of polycyclic aromatic hydrocarbons on water ice.

In dense interstellar environments, Polycyclic Aromatic Hydrocarbons (PAHs) are likely to condense onto or integrate into water ice mantles covering dust grains. Understanding the role of ice in the photo-induced processes involving adsorbed PAHs is therefore a key issue in astrochemistry. This requires (i) the knowledge of PAH-ice interactions, i.e. PAH-ice adsorption energies and local structures at the PAH-ice interface, as well as (ii) the understanding of the fate of electrons in the PAH-ice system upon excitation. Regarding (i), in this work, we determined the lowest energy structures of PAH-ice systems for a variety of PAHs ranging from naphthalene to ovalene on three types of ice - crystalline (Ih and Ic) and amorphous (low density) - using an explicit description of the electrons and a finite-sized system. The electronic structure was determined using the Self Consistent Charge Density Functional based Tight Binding (SCC-DFTB) scheme with modified Mulliken charges in order to ensure a good description of the studied systems. Regarding (ii), the influence of the interaction with ice on the Vertical Ionisation Potentials (VIPs) of the series of PAHs was determined using the constrained SCC-DFTB scheme benchmarked against correlated wavefunction results for PAH-(H2O)n (n = 1-6, 13) clusters. The results show a deviation equal, at most, to ∼1.4 eV of the VIPs of PAHs adsorbed on ice with respect to the gas phase values. Our results are discussed in the light of experimental data and previous theoretical studies.

The Electronic Structure of Beryllium Chains.

We present an ab initio theoretical study of quasi one-dimensional beryllium chains, Be N, from an electronic structure perspective for N = 3, 4,···, 12. In particular, linear and cyclic systems were compared by using high-quality coupled-cluster formalism. Both linear and cyclic species were found to be local minima on the corresponding potential energy surface, for all the considered values of N. The linear geometry is the most stable one only in the case of Be4. Several indicators (energy gap, position spread tensor, locality of the molecular orbitals) clearly show that both linear and cyclic one-dimensional structures, unlike three-dimensional bulk beryllium, have a covalent insulating nature.

Photochemistry of Fe:H2O Adducts in Argon Matrixes: A Combined Experimental and Theoretical Study in the Mid-IR and UV-Visible Regions.

The photochemistry of Fe:H2O adducts is of interest in fields as diverse as catalysis and astrochemistry. Industrially, iron can be used as a catalyst to convert H2O to H2, whereas in the interstellar medium it may be an important component of dust grains, influencing the chemistry on their icy surfaces. This study consisted of the deposition and spectral characterization of binary systems of atomic iron with H2O in cryogenic argon matrixes. In this way, we were able to obtain information about the interaction of the two species; we observed the formation of adducts of iron monomers and dimers with water molecules in the mid-IR and UV-visible spectral domains. Upon irradiation with a UV radiation source, the iron species were inserted into the water molecules to form HFeOH and HFe2OH, leading in some cases to the formation of FeO possibly accompanied by the production of H2. DFT and correlated multireference wave function calculations confirmed our attributions. This combination of IR and UV-visible spectroscopy with theoretical calculations allowed us to determine, for the first time, the spectral characteristics of iron adducts and their photoproducts in the UV-visible and in the OH stretching region of the mid-IR domain.

Low-lying excited states of model proteins: Performances of the CC2 method versus multireference methods.

A benchmark set of relevant geometries of a model protein, the N-acetylphenylalanylamide, is presented to assess the validity of the approximate second-order coupled cluster (CC2) method in studying low-lying excited states of such bio-relevant systems. The studies comprise investigations of basis-set dependence as well as comparison with two multireference methods, the multistate complete active space 2nd order perturbation theory (MS-CASPT2) and the multireference difference dedicated configuration interaction (DDCI) methods. First of all, the applicability and the accuracy of the quasi-linear multireference difference dedicated configuration interaction method have been demonstrated on bio-relevant systems by comparison with the results obtained by the standard MS-CASPT2. Second, both the nature and excitation energy of the first low-lying excited state obtained at the CC2 level are very close to the Davidson corrected CAS+DDCI ones, the mean absolute deviation on the excitation energy being equal to 0.1 eV with a maximum of less than 0.2 eV. Finally, for the following low-lying excited states, if the nature is always well reproduced at the CC2 level, the differences on excitation energies become more important and can depend on the geometry.

Electronic Spectroscopy of [FePAH](+) Complexes in the Region of the Diffuse Interstellar Bands: Multireference Wave Function Studies on [FeC6H6](+).

The low-energy states and electronic spectrum in the near-infrared-visible region of [FeC6H6](+) are studied by theoretical approaches. An exhaustive exploration of the potential energy surface of [FeC6H6](+) is performed using the density functional theory method. The ground state is found to be a (4)A1 state. The structures of the lowest energy states ((4)A2 and (4)A1) are used to perform multireference wave function calculations by means of the multistate complete active space with perturbation at the second order method. Contrary to the density functional theory results ((4)A1 ground state), multireference perturbative calculations show that the (4)A2 state is the ground state. The vertical electronic spectrum is computed and compared with the astronomical diffuse interstellar bands, a set of near-infrared-visible bands detected on the extinction curve in our and other galaxies. Many transitions are found in this domain, corresponding to d → d, d → 4s, or d → π* excitations, but few are allowed and, if they are, their oscillation strengths are small. Even though some band positions could match some of the observed bands, the relative intensities do not fit, making the contribution of the [Fe-C6H6](+) complexes to the diffuse interstellar bands questionable. This work, however, lays the foundation for the studies of polycyclic aromatic hydrocarbons (PAHs) complexed to Fe cations that are more likely to possess d → π* and π → π* transitions in the diffuse interstellar bands domain. PAH ligands indeed possess a larger number of π and π* orbitals, respectively, higher and lower in energy than those of C6H6, which are expected to lead to lower energy d → π* and π → π* transitions in [FePAH](+) than in [FeC6H6](+) complexes.

Magnetic coupling constants of self-assembled Cu(II) [3×3] grids: alternative spin model from theoretical calculations.

This paper reports a theoretical analysis of the electronic structure and magnetic properties of a ferromagnetic Cu(II) [3×3] grid. A two-step strategy, combining calculations on the whole grid and on binuclear fragments, has been employed to evaluate all the magnetic interactions in the grid. The calculations confirm an S = 7/2 ground state, which is in accordance with the magnetisation versus field curve and the thermal dependence of the magnetic moment data. Only the first-neighbour coupling terms present non-negligible amplitudes, all of them in agreement with the structure and arrangement of the Cu 3d magnetic orbitals. The results indicate that the dominant interaction in the system is the antiferromagnetic coupling between the ring and the central Cu sites (J3 = J4 ≈ -31 cm(-1)). In the ring two different interactions can be distinguished, J1 = 4.6 cm(-1) and J2 = -0.1 cm(-1), in contrast to the single J model employed in the magnetic data fit. The calculated J values have been used to determine the energy level distribution of the Heisenberg magnetic states. The effective magnetic moment versus temperature plot resulting from this ab initio energy profile is in good agreement with the experimental curve and the fitting obtained with the simplified spin model, despite the differences between these two spin models. This study underlines the role that the theoretical evaluations of the coupling constants can play on the rationalisation of the magnetic properties of these complex polynuclear systems.

X-ray crystallographic analysis of the antiferromagnetic low-temperature phase of galvinoxyl: investigating magnetic duality in organic radicals.

Galvinoxyl, as one of the most extensively studied organic stable free radicals, exhibits a notable phase transition from a high-temperature (HT) phase with a ferromagnetic (FM) intermolecular interaction to a low-temperature (LT) phase with an antiferromagnetic (AFM) coupling at 85 K. Despite significant research efforts, the crystal structure of the AFM LT phase has remained elusive. This study successfully elucidates the crystal structure of the LT phase, which belongs to the P1̄ space group. The crystal structure of the LT phase is found to consist of a distorted dimer, wherein the distortion arises from the formation of short intermolecular distances between anti-node carbons in the singly-occupied molecular orbital (SOMO). Starting from the structure of the LT phase, wave function calculations show that the AFM coupling 2J/kB varies significantly from -1069 K to -54 K due to a parallel shift of the molecular planes within the dimer.

Functional insulin therapy in type 1 diabetics: Short-term effects on weight and nutritional intake.

INTRODUCTION-AIM: Flexible insulin therapy is currently considered the gold standard therapy of type 1 diabetes. We aimed to study the evolution of glycemic control, weight and nutritional intake of a group of patients with type 1 diabetes, three months after the initiation of functional insulin therapy (FIT). METHODS: This was a prospective longitudinal study having included 30 type 1 diabetic patients hospitalized for education to FIT. Each patient underwent an assessment of glycemic control (glycated hemoglobin (A1C) and number of hypoglycemia), weight and nutritional intake before FIT and 3 months after the initiation of this educative approach. RESULTS: The mean age of patients was 21,8 ± 7,9 years and the sex ratio was 0,5. The mean duration of diabetes was 7,2 ± 6 years. Three months after initiation of FIT, we observed a significant lowering of A1C, which went from 9,2 ± 1,6% to 8,3 ± 1,4% (p<0,001) of the number of minor hypoglycemia (p=0,001) and that of severe hypoglycemia (p= 0,021). the average weight went from 64,6 ± 13,1 kg to 65,5 ± 13,5 kg (p = 0,040) with a significant increase in BMI (p = 0,041). Weight gain was observed in 67% of patients. This weight gain contrasted with a significant decrease in caloric (p = 0,040) and in carbohydrates intakes (p = 0,027). CONCLUSION: Weight gain, associated with better glycemic control, should encourage the healthcare team to strengthen therapeutic education of patients undergoing FIT in order to limit weight gain.