Multi-layer Gaussian-based multi-configuration time-dependent Hartree (ML-GMCTDH) simulations of ultrafast charge separation in a donor–acceptor complex

We report on first applications of the Multi-Layer Gaussian-based Multi-Configuration Time-Dependent Hartree (ML-GMCTDH) method [Römer et al., J. Chem. Phys. 138, 064106 (2013)] beyond its basic two-layer variant. The ML-GMCTDH scheme provides an embedding of a variationally evolving Gaussian wavepacket basis into a hierarchical tensor representation of the wavefunction. A first-principles parameterized model Hamiltonian for ultrafast non-adiabatic dynamics in an oligothiophene–fullerene charge transfer complex is employed, relying on a two-state linear vibronic coupling model that combines a distribution of tuning type modes with an intermolecular coordinate that also modulates the electronic coupling. Efficient ML-GMCTDH simulations are carried out for up to 300 vibrational modes using an implementation within the QUANTICS program. Excellent agreement with reference ML-MCTDH calculations is obtained

The Gas Sensing Properties of Porphyrins-coated Laterally Grown ZnO Nanorods

AbstractPorphyrins coated ZnO is an interesting material where the exposure to light and gas may cooperate to modulate the respective sensitivities. In this work, the gas sensing properties of porphyrins functionalized laterally grown ZnO nanorods are introduced. The porphyrin layer incompletely coats the semiconductor surface in order to keep both ZnO and porphyrins in contact with analyte. It is known that UV light may prompt the chemical sensitivity of ZnO replacing the high temperature condition. Here we demonstrate that because of the photo-injection of electrons from porphyrin to the ZnO, the same impact could be acquired with visible light

New understandings of the genetic basis of isolated idiopathic central hypogonadism

Idiopathic hypogonadotropic hypogonadism is a rare disease that is characterized by delayed/absent puberty and/or infertility due to an insufficient stimulation of an otherwise normal pituitary-gonadal axis by gonadotrophin-releasing hormone (GnRH) action. Because reduced or normal luteinizing hormone (LH)/follicle-stimulating hormone (FSH) levels may be observed in the affected patients, the term idiopathic central hypogonadism (ICH) appears to be more appropriate. This disease should be distinguished from central hypogonadism that is combined with other pituitary deficiencies. Isolated ICH has a complex pathogenesis and is fivefold more prevalent in males. ICH frequently appears in a sporadic form, but several familial cases have also been reported. This finding, in conjunction with the description of numerous pathogenetic gene variants and the generation of several knockout models, supports the existence of a strong genetic component. ICH may be associated with several morphogenetic abnormalities, which include osmic defects that, with ICH, constitute the cardinal manifestations of Kallmann syndrome (KS). KS accounts for approximately 40% of the total ICH cases and has been generally considered to be a distinct subgroup. However, the description of several pedigrees, which include relatives who are affected either with isolated osmic defects, KS, or normo-osmic ICH (nICH), justifies the emerging idea that ICH is a complex genetic disease that is characterized by variable expressivity and penetrance. In this context, either multiple gene variants or environmental factors and epigenetic modifications may contribute to the variable disease manifestations. We review the genetic mechanisms that are presently known to be involved in ICH pathogenesis and provide a clinical overview of the 227 cases that have been collected by the collaborating centres of the Italian ICH Network

The Hi-GAL compact source catalogue – I. The physical properties of the clumps in the inner Galaxy (−71. ◦ 0 < ℓ < 67.◦ 0)

Hi-GAL (Herschel InfraRed Galactic Plane Survey) is a large-scale survey of the Galactic plane, performed with Herschel in five infrared continuum bands between 70 and 500 µm. We present a band-merged catalogue of spatially matched sources and their properties derived from fits to the spectral energy distributions (SEDs) and heliocentric distances, based on the photometric catalogues presented in Molinari et al., covering the portion of Galactic plane −71.◦ 0 < ℓ < 67.◦ 0. The band-merged catalogue contains 100 922 sources with a regular SED, 24 584 of which show a 70-µm counterpart and are thus considered protostellar, while the remainder are considered starless. Thanks to this huge number of sources, we are able to carry out a preliminary analysis of early stages of star formation, identifying the conditions that characterize different evolutionary phases on a statistically significant basis. We calculate surface densities to investigate the gravitational stability of clumps and their potential to form massive stars. We also explore evolutionary status metrics such as the dust temperature, luminosity and bolometric temperature, finding that these are higher in protostellar sources compared to pre-stellar ones. The surface density of sources follows an increasing trend as they evolve from pre-stellar to protostellar, but then it is found to decrease again in the majority of the most evolved clumps. Finally, we study the physical parameters of sources with respect to Galactic longitude and the association with spiral arms, finding only minor or no differences between the average evolutionary status of sources in the fourth and first Galactic quadrants, or between 'on-arm' and 'interarm' positions

Hi-GAL: The Herschel Infrared Galactic Plane Survey

Hi-GAL, the Herschel infrared Galactic Plane Survey, is an Open Time Key Project of the Herschel Space Observatory. It will make an unbiased photometric survey of the inner Galactic plane by mapping a 2° wide strip in the longitude range midlmid < 60° in five wavebands between 70 μm and 500 μm. The aim of Hi-GAL is to detect the earliest phases of the formation of molecular clouds and high-mass stars and to use the optimum combination of Herschel wavelength coverage, sensitivity, mapping strategy, and speed to deliver a homogeneous census of star-forming regions and cold structures in the interstellar medium. The resulting representative samples will yield the variation of source temperature, luminosity, mass and age in a wide range of Galactic environments at all scales from massive YSOs in protoclusters to entire spiral arms, providing an evolutionary sequence for the formation of intermediate and high-mass stars. This information is essential to the formulation of a predictive global model of the role of environment and feedback in regulating the star-formation process. Such a model is vital to understanding star formation on galactic scales and in the early universe. Hi-GAL will also provide a science legacy for decades to come with incalculable potential for systematic and serendipitous science in a wide range of astronomical fields, enabling the optimum use of future major facilities such as JWST and ALMA

Hi-GAL: The Herschel Infrared Galactic Plane Survey

Hi-GAL, the Herschel infrared Galactic Plane Survey, is an Open Time Key Project of the Herschel Space Observatory. It will make an unbiased photometric survey of the inner Galactic plane by mapping a 2° wide strip in the longitude range ∣l∣ < 60° in five wavebands between 70 μm and 500 μm. The aim of Hi-GAL is to detect the earliest phases of the formation of molecular clouds and high-mass stars and to use the optimum combination of Herschel wavelength coverage, sensitivity, mapping strategy, and speed to deliver a homogeneous census of star-forming regions and cold structures in the interstellar medium. The resulting representative samples will yield the variation of source temperature, luminosity, mass and age in a wide range of Galactic environments at all scales from massive YSOs in protoclusters to entire spiral arms, providing an evolutionary sequence for the formation of intermediate and high-mass stars. This information is essential to the formulation of a predictive global model of the role of environment and feedback in regulating the star-formation process. Such a model is vital to understanding star formation on galactic scales and in the early universe. Hi-GAL will also provide a science legacy for decades to come with incalculable potential for systematic and serendipitous science in a wide range of astronomical fields, enabling the optimum use of future major facilities such as JWST and ALMA

The fate of molecular excited states: modeling donor-acceptor dyes

We investigate the relaxation of a coherently excited molecule in the Redfield approximation. The molecular model, parametrized to describe donor-acceptor dyes that represent a large family of molecules of interest for several applications, accounts for two diabatic electronic states non-adiabatically coupled to a few vibrational coordinates. The proposed approach successfully describes the fast vibrational relaxation, followed by a much slower relaxation towards the ground state, a physically relevant result that is robust vs. the specific model adopted for the system-bath coupling and the specific (reasonable) choice of the bath spectral density. We demonstrate that, when dealing with more than a single vibration, it is important that each vibration is separately coupled to an independent bath so as to avoid the cross-talking of the modes through their coupling to the same bath. Provided that the overall strength of the electron-vibration coupling is maintained constant, the number of molecular vibrations introduced in the model does not affect the system dynamics, supporting the use of effective and easy models for donor-acceptor dyes accounting for a single coupled vibration

Vibrational coherences in charge-transfer dyes: A non-adiabatic picture

Essential-state models efficiently describe linear and nonlinear spectral properties of different families of charge-transfer chromophores. Here, the essential-state machinery is applied to the calculation of the early-stage dynamics after ultrafast (coherent) excitation of polar and quadrupolar chromophores. The fully non-adiabatic treatment of coupled electronic and vibrational motion allows for a reliable description of the dynamics of these intriguing systems. In particular, the proposed approach is reliable even when the adiabatic and harmonic approximations do not apply, such as for quadrupolar dyes that show a multistable, broken-symmetry excited state. Our approach quite naturally leads to a clear picture for a dynamical Jahn-Teller effect in these systems. The recovery of symmetry due to dynamical effects is however disrupted in polar solvents where a static symmetry lowering is observed. More generally, thermal disorder in polar solvents is responsible for dephasing phenomena, damping the coherent oscillations with particularly important effects in the case of polar dyes