Application to nonlinear optical properties of the RSX-QIDH double-hybrid range-separated functional.

The effective calculation of static nonlinear optical properties requires a considerably high accuracy at a reasonable computational cost, to tackle challenging organic and inorganic systems acting as precursors and/or active layers of materials in (nano-)devices. That trade-off implies to obtain very accurate electronic energies in the presence of externally applied electric fields to consequently obtain static polarizabilities ( α i j ) and hyper-polarizabilities ( ß i j k and γ i j k l ). Density functional theory is known to provide an excellent compromise between accuracy and computational cost, which is however largely impeded for these properties without introducing range-separation techniques. We thus explore here the ability of a modern (double-hybrid and range-separated) Range-Separated eXchange Quadratic Integrand Double-Hybrid exchange-correlation functional to compete in accuracy with more costly and/or tuned methods, thanks to its robust and parameter-free nature.

Accessible interferometric autocorrelator for noise-like pulses based on a Fabry-Perot cavity.

In this work, we develop experimentally a Fabry-Perot fiber optic interferometer applied to the measurement of autocorrelation of complex dynamic pulses generated by a figure-eight fiber laser. The principle is based in the superposition of multiple pulses, which requires two partially reflecting flat surfaces in parallel, resulting in a simple and compact autocorrelator design. The autocorrelation trace obtained exhibits a typical double-scaled structure for noise-like pulses (NLPs), with an ultrashort coherence spur on the order of 100 fs riding upon a broad pedestal of 120 ps. Finally, we show experimentally that the developed Fabry-Perot device is able to measure accurately the autocorrelation of NLPs, as confirmed by comparing the measurement with that of a conventional autocorrelator scheme based on a Michelson interferometer, with the additional advantages of a more compact setup and a much easier alignment procedure compared to the latter.

Correlation vs. exchange competition drives the singlet-triplet excited-state inversion in non-alternant hydrocarbons.

In this work, we focus on the understanding of the driving force behind the S1-T1 excited-state energy inversion (which would thus violate Hund's rule, making the S1 state lower in energy than the T1 state) of two non-benzenoid non-alternant hydrocarbons, composed of odd-membered rings. The molecules considered here have identical chemical composition but different atomic configuration in space. The delicate interplay between structural and electronic factors that might induce inversion and its energy extension, only by a few meV, is systematically investigated here by state-of-the-art calculations. Qualitative and quantitative accurate predictions are obtained employing post-HF methods, thanks to the balanced and careful inclusion of electron correlation effects. The obtained results might guide and rationalize new searches for molecules violating Hund's rule, concomitantly demonstrating the importance of key contributions from the theoretical method of choice.

Electronic structure of rhombus-shaped nanographenes: system size evolution from closed- to open-shell ground states.

We theoretically study and characterize a set of rhombus-shaped nanographenes of increasing size, or n-rhombenes, where n = 2-6, displaying zigzag edges leading to an enhancement of the (poly)radicaloid nature and the appearance of intrinsic magnetism as a function of n. Due to that system-dependent radicaloid nature, we employ spin-flip methods able to capture the challenging physics of the problem, thus providing accurate energy differences between high- and low-spin solutions. The theoretical predictions agree with the experimentally available magnetic exchange coupling for the recently synthesized 5-rhombene, as well as with the size at which the transition from a closed-shell to an open-shell ground-state solution occurs. We also investigate if standard DFT methods are able to reproduce the trend disclosed by spin-flip methods and if the results are highly dependent on the functional choice and/or the intrinsic spin contamination.

Excitation energies of polycylic aromatic hydrocarbons by double-hybrid functionals: Assessing the PBE0-DH and PBE-QIDH models and their range-separated versions.

A family of non-empirical double-hybrid (DH) density functionals, such as Perdew-Burke-Ernzerhof (PBE)0-DH, PBE-QIDH, and their range-separated exchange (RSX) versions RSX-0DH and RSX-QIDH, all using Perdew-Burke-Ernzerhof(PBE) exchange and correlationfunctionals, is applied here to calculate the excitation energies for increasingly longer linear and cyclic acenes as part of their intense benchmarking for excited states of all types. The energies for the two lowest-lying singlet 1La and 1Lb states of linear oligoacenes as well as the triplet 3La and 3Lb states, are calculated and compared with experimental results. These functionals clearly outperform the results obtained from hybrid functionals and favorably compare with other double-hybrid expressions also tested here, such as B2-PLYP, B2GP-PLYP, ωB2-PLYP, and ωB2GP-PLYP. The study is complemented by the computation of adiabatic S0-T1 singlet-triplet energy difference for linear acenes as well as the extension of the study to strained cyclic oligomers, showing how the family of non-empirical expressions robustly leads to competitive results.

Assessment of the nonempirical r2SCAN-QIDH double-hybrid density functional against large and diverse datasets.

We update the Quadratic Integrand Double-Hybrid (QIDH) model [J. Chem. Phys. 141, 031101 (2014)] by incorporating the nonempirical restored-regularized Strongly Constrained and Appropriately Normed (r2SCAN) meta-generalized gradient approximation exchange-correlation functional, thus devising a robust density functional approximation free of any empirical parameter and incorporating all the constraints so far known for the exchange-correlation kernel. We assessed the new r2SCAN-QIDH expression on the GMTKN55 database and further extend its application to various types of non-covalent interactions (e.g., S66 × 8, O24 × 5). The assessment done shows that the model becomes very competitive in accuracy with respect to parent exchange-correlation functionals of any type, but without relying on any fitted parameter or numerical training.

Stability of the polyynic form of C18, C22, C26, and C30 nanorings: a challenge tackled by range-separated double-hybrid density functionals.

We calculate the relative energy between the cumulene and polyyne structures of a set of C4k+2 (k = 4-7) rings (C18, C22, C26, and C30 prompted by the recent synthesis of the cyclo[18]carbon (or simply C18) compounds. Reference results were obtained by a costly Quantum Monte-Carlo (QMC) approach, providing thus very accurate values allowing to systematically compare the performance of a variety of wavefunction methods [(i.e., MP2, SCS-MP2, SOS-MP2, DLPNO-CCSD, and DLPNO-CCSD(T)] as well as DFT approaches, applying for the latter a diversity of density functionals covering global and range-separated hybrid and double-hybrid models. The influence of the use of a range-separation scheme for density functionals, for both hybrid and double-hybrid expressions, is discussed according to its key role. Overall, range-separated double-hybrid functionals (e.g., RSX-QIDH) behave very accurately and provide competitive results compared with DLPNO-CCSD(T), at a more reasonable computational cost.

Violation of Hund's rule in molecules: Predicting the excited-state energy inversion by TD-DFT with double-hybrid methods.

The energy difference (ΔEST) between the lowest singlet (S1) state and the triplet (T1) excited state of a set of azaphenalene compounds, which is theoretically and experimentally known to violate Hund's rule, giving rise to the inversion of the order of those states, is calculated here with a family of double-hybrid density functionals. That excited-state inversion is known to be very challenging to reproduce for time-dependent density functional theory employing common functionals, e.g., hybrid or range-separated expressions, but not for wavefunction methods due to the inclusion of higher-than-single excitations. Therefore, we explore here if the last developed family of density functional expressions (i.e., double-hybrid models) is able to provide not only the right excited-state energy order but also accurate ΔEST values, thanks to the approximate inclusion of double excitations within these models. We herein employ standard double-hybrid (B2-PLYP, PBE-QIDH, and PBE0-2), range-separated (ωB2-PLYP and RSX-QIDH), spin-scaled (SCS/SOS-B2PLYP21, SCS-PBE-QIDH, and SOS-PBE-QIDH), and range-separated spin-scaled (SCS/SOS-ωB2-PLYP, SCS-RSX-QIDH, and SOS-RSX-QIDH) expressions to systematically assess the influence of the ingredients entering into the formulation while concomitantly providing insights for their accuracy.

Dietary diversity and depression: cross-sectional and longitudinal analyses in Spanish adult population with metabolic syndrome. Findings from PREDIMED-Plus trial.

OBJECTIVE: To examine the cross-sectional and longitudinal (2-year follow-up) associations between dietary diversity (DD) and depressive symptoms. DESIGN: An energy-adjusted dietary diversity score (DDS) was assessed using a validated FFQ and was categorised into quartiles (Q). The variety in each food group was classified into four categories of diversity (C). Depressive symptoms were assessed with Beck Depression Inventory-II (Beck II) questionnaire and depression cases defined as physician-diagnosed or Beck II >= 18. Linear and logistic regression models were used. SETTING: Spanish older adults with metabolic syndrome (MetS). PARTICIPANTS: A total of 6625 adults aged 55-75 years from the PREDIMED-Plus study with overweight or obesity and MetS. RESULTS: Total DDS was inversely and statistically significantly associated with depression in the cross-sectional analysis conducted; OR Q4 v. Q1 = 0·76 (95 % CI (0·64, 0·90)). This was driven by high diversity compared to low diversity (C3 v. C1) of vegetables (OR = 0·75, 95 % CI (0·57, 0·93)), cereals (OR = 0·72 (95 % CI (0·56, 0·94)) and proteins (OR = 0·27, 95 % CI (0·11, 0·62)). In the longitudinal analysis, there was no significant association between the baseline DDS and changes in depressive symptoms after 2 years of follow-up, except for DD in vegetables C4 v. C1 = (ß = 0·70, 95 % CI (0·05, 1·35)). CONCLUSIONS: According to our results, DD is inversely associated with depressive symptoms, but eating more diverse does not seem to reduce the risk of future depression. Additional longitudinal studies (with longer follow-up) are needed to confirm these findings.

Singlet-Triplet Excited-State Inversion in Heptazine and Related Molecules: Assessment of TD-DFT and ab initio Methods.

We have investigated the origin of the S1 -T1 energy levels inversion for heptazine, and other N-doped π-conjugated hydrocarbons, leading thus to an unusually negative singlet-triplet energy gap ( ΔEST<0 ). Since this inversion might rely on substantial doubly-excited configurations to the S1 and/or T1 wavefunctions, we have systematically applied multi-configurational SA-CASSCF and SC-NEVPT2 methods, SCS-corrected CC2 and ADC(2) approaches, and linear-response TD-DFT, to analyze if the latter method could also face this challenging issue. We have also extended the study to B-doped π-conjugated systems, to see the effect of chemical composition on the results. For all the systems studied, an intricate interplay between the singlet-triplet exchange interaction, the influence of doubly-excited configurations, and the impact of dynamic correlation effects, serves to explain the ΔEST<0 values found for most of the compounds, which is not predicted by TD-DFT.

peri-Acenoacene molecules: tuning of the singlet and triplet excitation energies by modifying their radical character.

The energy difference between singlet and triplet excitons, or ΔEST, is a key parameter for novel light-emission mechanisms (i.e., TADF or thermally activated delayed fluorescence) or other photoactivated processes. We have studied a set of conjugated molecules (peri-acenoacenes and their heteroatom-doped analogues) to observe the evolution of their excited-state properties upon increasing the system size with and without substitution with a pair of N atoms. Since these molecules exhibit a (ground-state) diradicaloid character, together with marked correlation effects influencing the excited-states formed, we have applied a variety of theoretical methods (FT-DFT, TD-DFT, SF-TD-DFT, CIS, CIS(D), SCS-CC2, SA-CASSCF, and SC-NEVPT2) to bracket the accuracy of the results while concomitantly providing insights into electronic structure. The results show how this chemical strategy (N-doping) largely modifies not only the excited-state energies but also the oscillator strengths and the ΔEST values, constituting versatile platforms for fine-tuned photophysical applications.

Negative Singlet-Triplet Excitation Energy Gap in Triangle-Shaped Molecular Emitters for Efficient Triplet Harvesting.

The full harvesting of both singlet and triplet excitons can pave the way toward more efficient molecular light-emission mechanisms (i.e., TADF or thermally activated delayed fluorescence) beyond the spin statistics limit. This TADF mechanism benefits from low (but typically positive) singlet-triplet energy gaps or ΔEST. Recent research has suggested the possibility of inverting the order of the energy of lowest singlet and triplet excited states, thus opening new pathways to promote light emission without any energy barrier through triplet to singlet conversion, which is systematically investigated here by means of theoretical methods. To this end, we have selected a set of heteroatom-substituted triangle-shaped molecules (or triangulenes) for which ΔEST < 0 is predicted. We successfully rationalize the origin of that energy inversion and the reasons for which theoretical methods might produce qualitatively inconsistent predictions depending on how they treat n-tuple excitations (e.g., the large contribution of double excitations for all of the ground and excited states involved). Unfortunately, the time-dependent density functional theory method is unable to deal with the physical effects driving this behavior, which prompted us to use more sophisticated ab initio methods here such as SA-CASSCF, SC-NEVPT2, SCS-CC2, and SCS-ADC(2).

Precision Nanotube Mimics via Self-Assembly of Programmed Carbon Nanohoops.

The scalable production of homogeneous, uniform carbon nanomaterials represents a key synthetic challenge for contemporary organic synthesis as nearly all current fabrication methods provide heterogeneous mixtures of various carbonized products. For carbon nanotubes (CNTs) in particular, the inability to access structures with specific diameters or chiralities severely limits their potential applications. Here, we present a general approach to access solid-state CNT mimic structures via the self-assembly of fluorinated nanohoops, which can be synthesized in a scalable, size-selective fashion. X-ray crystallography reveals that these CNT mimics exhibit uniform channel diameters that are precisely defined by the diameter of their nanohoop constituents, which self-assemble in a tubular fashion via a combination of arene-pefluoroarene and C-H-F interactions. The nanotube-like assembly of these systems results in capabilities such as linear guest alignment and accessible channels, both of which are observed in CNTs but not in the analogous all-hydrocarbon nanohoop systems. Calculations suggest that the organofluorine interactions observed in the crystal structure are indeed critical in the self-assembly and robustness of the CNT mimic systems. This work establishes the self-assembly of carbon nanohoops via weak interactions as an attractive means to generate solid-state materials that mimic carbon nanotubes, importantly with the unparalleled tunability enabled by organic synthesis.

Nature (Hole or Electron) of Charge-Transfer Ability of Substituted Cyclopyrenylene Hoop-Shaped Compounds.

We theoretically investigate here by means of DFT methods how the selective substitution in cyclic organic nanorings composed of pyrene units may promote semiconducting properties, analyzing the energy needed for a hole- or electron-transfer accommodation as a function of the substitution pattern and the system size (i.e., number of pyrene units). We choose to study both [3]Cyclo-2,7-pyrenylene ([3]CPY) and [4]Cyclo-2,7-pyrenylene ([4]CPY) compounds, the latter already synthesized, with substituents other than hydrogen acting in ipso and ortho positions, as well as the effect of the per-substitution. As substituents, we selected a set of electroactive halogen atoms (F, Cl, and Br) and groups (CN) to disclose structure-property relationships allowing thus to anticipate the use of these systems as organic molecular semiconductors.

Biological mesh reconstruction versus primary closure for preventing perineal morbidity after extralevator abdominoperineal excision: a multicentre retrospective study.

AIM: The aim of the study was to compare the incidence of perineal hernia and the perineal wound morbidity following extralevator abdominoperineal excision (ELAPE) between two groups - primary perineal closure and reconstruction with a biological mesh. METHOD: One hundred and forty-seven consecutive patients who underwent ELAPE for primary rectal cancer between January 2007 and December 2018 in two tertiary referral centres were retrospectively identified from prospective databases. Perineal closure was carried out via primary closure or with a biological mesh (porcine dermal collagen mesh). Outcome measures were perineal hernia and perineal wound morbidity (infection, dehiscence, persistent sinus and chronic pain). RESULTS: A total of 139 patients were included in the study. A prophylactic mesh was used in 80 (57.5%) and primary closure was practised in 59 (42.4%) patients. The median follow-up was 30 (interquartile range 46.88) months. Thirty patients (21.6%) developed perineal hernia. No significant differences were found between prophylactic mesh and primary closure (16.3% vs 23.3%, P = 0.07). The median period between surgery and hernia diagnosis was 8 months in the primary closure group and 24 months in the mesh group (P < 0.01). Perineal wound morbidity was significantly higher in the prophylactic mesh group (55% vs 33.9%, P < 0.01). CONCLUSION: In our study, the use of a biological mesh did not reduce the rate of perineal hernia, although it did delay its appearance. Perineal closure using a biological mesh may increase perineal morbidity, both acute and chronic.

Numerical study of complex dynamics and extreme events within noise-like pulses from an erbium figure-eight laser.

Some complex dissipative dynamics associated with the noise-like pulse (NLP) regime of a passively mode-locked erbium-doped fiber laser are studied numerically. By means of a convenient 3D mapping of the spatio-temporal pulse evolution, for properly chosen dispersion parameters, several puzzling dissipative dynamics of NLPs are identified, including the expelling of sub-packets that move away from the main bunch, the sudden extinction of isolated sub-pulses, the collision between different internal fragments travelling at different speeds, the rising of sub-pulses, the formation of complex trajectories by substructures that first move away and then return to the main bunch, and so on. In addition, the emergence of optical rogue waves (ORWs) within NLPs is also demonstrated numerically; to help understand these behaviors evidenced in the time domain, spectral analyzes were also performed that show, among other things, that the spectrum of a NLP is notoriously distorted when it hosts an ORW phenomenon. These numerical results are consistent with previously published experimental results.

Gain-driven spectral-temporal noise-like pulse dynamics in a passively mode-locked fiber laser.

We study numerically complex noise-like pulse dynamics in a passively mode-locked erbium-doped fiber laser. Wavelength-dependent gain dynamics is modeled as a combination of a three-level and a four-level system, which approximate the gain behavior in the 1530-nm and 1560-nm regions, respectively. The typical deformation of the erbium gain spectrum as it saturates is properly reproduced by this approach. Several puzzling noise-like pulse dynamics that were recently observed experimentally are qualitatively reproduced numerically, in particular slow quasi-periodic energy variations and the emergence and walkoff of wavelength-shifted radiation components. These results clearly reveal that gain dynamics is deeply involved in the onset of such complex temporal and spectral instabilities in these sources.

Simultaneous temporal and spectral analysis of noise-like pulses in a mode-locked figure-eight fiber laser.

We present an experimental study of complex noise-like pulse dynamics in a passively mode-locked figure-eight fiber laser, by performing simultaneous temporal and spectral mapping of the waveform sequences. The simultaneous measurements allow us to relate temporal and spectral events. We found in particular that the evolution of energy and of temporal features such as the number and width of the wave packets is correlated to spectral variations, namely of the central wavelength and bandwidth of the instantaneous spectrum. The simultaneous temporal and spectral measurements also allowed a substantial improvement in the precision of the latter, which was performed using the dispersive Fourier transform method. In particular, this enhanced precision allowed measuring the subtle spectral differences between the two laser outputs and tracking their evolution over the cycles, providing crucial information that allowed to determine the physical phenomena involved in the observed dynamics.

From cyclic nanorings to single-walled carbon nanotubes: disclosing the evolution of their electronic structure with the help of theoretical methods.

We systematically investigate the relationships between structural and electronic effects of finite size zigzag or armchair carbon nanotubes of various diameters and lengths, starting from a molecular template of varying shape and diameter, i.e. cyclic oligoacene or oligophenacene molecules, and disclosing how adding layers and/or end-caps (i.e. hemifullerenes) can modify their (poly)radicaloid nature. We mostly used tight-binding and finite-temperature density-based methods, the former providing a simple but intuitive picture about their electronic structure, and the latter dealing effectively with strong correlation effects by relying on a fractional occupation number weighted electron density (ρFOD), with additional RAS-SF calculations backing up the latter results. We also explore how minor structural modifications of nanotube end-caps might influence the results, showing that topology, together with the chemical nature of the systems, is pivotal for the understanding of the electronic properties of these and other related systems.

Neurological presentations of Bartonella henselae infection.

OBJECTIVE: Neurological symptoms in patients with cat-scratch disease (CSD) have been rarely reported. The aim of this study is to analyze the frequency of neurological CSD (NCSD) and describe the disease clinical presentation, management and outcome. MATERIAL AND METHODS: We retrospectively selected patients with a CSD syndrome and Bartonella IgG titers > 1:256. Data regarding epidemiological, clinical, management, and follow-up features were analyzed and discussed. A comparison between NCSD and non-neurological CSD (NNCSD) was established. RESULTS: Thirty-nine CSD patients were selected. NCSD frequency was 10.25%. No children were found affected in the NCSD group. A 65.7% of NNCSD and the entirety of the NCSD group had a history of cat exposure. Immunosuppression was only present in the NNCSD group (8.6%). NCSD presentations were as follows: isolated aseptic meningitis (25%), neuroretinitis (50%), and isolated optic neuritis (25%). A greater proportion of patients in the NCSD group had fever and raised levels of acute phase reactants and white blood cells. 85.7% of NNCSD had a complete recovery, whereas only 50% of the NCSD patients experienced a full recovery. CONCLUSION: NCSD may be a distinctive group compared to NNCSD due to its later age of presentation, the more intense systemic response, and the poorer outcome.