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We propose a real-time time-dependent ab initio approach within a configuration-interaction-singles ansatz to decompose the high-harmonic generation (HHG) signal of molecules in terms of individual molecular-orbital (MO) contributions. Calculations have been performed by propagating the time-dependent Schrödinger equation with complex energies, in order to account for ionization of the system, and by using tailored Gaussian basis sets for high-energy and continuum states. We have studied the strong-field electron dynamics and the HHG spectra in aligned CO2 and H2O molecules. Contribution from MOs in the strong-field dynamics depends on the interplay between the MO ionization energy and the coupling between the MO and the laser-pulse symmetries. Such contributions characterize different portions of the HHG spectrum, indicating that the orbital decomposition encodes nontrivial information on the modulation of the strong-field dynamics. Our results correctly reproduce the MO contributions to HHG for CO2 as described in the literature experimental and theoretical data and lead to an original analysis of the role of the highest occupied molecular orbitals HOMO, HOMO-1, and HOMO-2 of H2O according to the polarization direction of the laser pulse. [ABSTRACT FROM AUTHOR]

We present a multiscale method coupling the theory of open quantum systems with real-time ab initio treatment of electronic structure to study hot-carrier dynamics in photoexcited plasmonic systems. We combine the Markovian Stochastic Schrödinger equation with an ab initio GW coupled to the Bethe–Salpeter (BSE) equation description of the electronic degrees of freedom, interacting with a metallic nanoparticle modeled classically according to the polarizable continuum model. We apply this methodology to study the effect of relaxation (T1) and pure dephasing (T2) times on the hot-carrier dynamics in a system composed of a quantum portion described at GW/BSE level, i.e., a CHO fragment adsorbed on a vertex of a rhodium nanocube, and of the rest of the nanocube, treated classically, when irradiated with a 2.7 eV light pulse, inspired by the experimental results on plasmon-driven CO2 photoreduction. A net hole injection from rhodium to CHO is observed, with and without the classical portion of the nanocube. The nanocube effect is to enhance the generated charge population by two orders of magnitude. The nonradiative decay, via a relaxation time T1 based on the energy-gap law, produces a rapid decrease of the charge population. Results with T2 only show that a charge injection retarded with respect to the pulse, which is present in the coherent dynamics, disappears when coherence is erased. [ABSTRACT FROM AUTHOR]

Following changes in chirality can give access to relevant information on the function or reactivity of molecular systems. Time-resolved circular dichroism (TRCD) spectroscopy proves to be a valid tool to achieve this goal. Depending on the class of molecules, different temporal ranges, spanning from seconds to femtoseconds, need to be investigated to observe such chiroptical changes. Therefore, over the years, several approaches have been adopted to cover the timescale of interest, especially based on pump–probe schemes. Moreover, various theoretical approaches have been proposed to simulate and explain TRCD spectra, including linear and non-linear response methods as well as non-adiabatic molecular dynamics. In this review, an overview on both experimental and theoretical advances in the TRCD field is provided, together with selected applications. A discussion on future theoretical developments for TRCD is also given. [ABSTRACT FROM AUTHOR]

Background KBG syndrome is caused by haploinsufficiency of ANKRD11 and 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. Methods CNS 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. Results We 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. Conclusion This 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 ANKRD11 variants in skeletal and brain development. [ABSTRACT FROM AUTHOR]

This study arises from the attempt to answer the following question: how different descriptions of electronic exchange and correlation affect the high-harmonic generation (HHG) spectroscopy of H2, N2, and CO2 molecules? We compare HHG spectra for H2, N2, and CO2 with different ab initio electronic structure methods: real-time time-dependent configuration interaction and real-time time-dependent density functional theory (RT-TDDFT) using truncated basis sets composed of correlated wave functions expanded on Gaussian basis sets. In the framework of RT-TDDFT, we employ Perdew-Burke-Ernzerhof (PBE) and long-range corrected Perdew-Burke-Ernzerhof (LC-ωPBE) functionals. We study HHG spectroscopy by disentangling the effect of electronic exchange and correlation. We first analyze the electronic exchange alone, and in the case of RT-TDDFT with LC-ωPBE, we use ω = 0.3 and ω = 0.4 to tune the percentage of long-range Hartree–Fock exchange and short-range exchange PBE. Then, we added the correlation as described by the PBE functional. All the methods give very similar HHG spectra, and they seem not to be particularly sensitive to the different description of exchange and correlation or to the correct asymptotic behavior of the Coulomb potential. Despite this general trend, some differences are found in the region connecting the cutoff and the background. Here, the harmonics can be resolved with different accuracy depending on the theoretical schemes used. We believe that the investigation of the molecular continuum and its coupling with strong fields merits further theoretical investigations in the near future. [ABSTRACT FROM AUTHOR]

TurboRVB is a computational package for ab initio Quantum Monte Carlo (QMC) simulations of both molecular and bulk electronic systems. The code implements two types of well established QMC algorithms: Variational Monte Carlo (VMC) and diffusion Monte Carlo in its robust and efficient lattice regularized variant. A key feature of the code is the possibility of using strongly correlated many-body wave functions (WFs), capable of describing several materials with very high accuracy, even when standard mean-field approaches [e.g., density functional theory (DFT)] fail. The electronic WF is obtained by applying a Jastrow factor, which takes into account dynamical correlations, to the most general mean-field ground state, written either as an antisymmetrized geminal power with spin-singlet pairing or as a Pfaffian, including both singlet and triplet correlations. This WF can be viewed as an efficient implementation of the so-called resonating valence bond (RVB) Ansatz, first proposed by Pauling and Anderson in quantum chemistry [L. Pauling, The Nature of the Chemical Bond (Cornell University Press, 1960)] and condensed matter physics [P.W. Anderson, Mat. Res. Bull 8, 153 (1973)], respectively. The RVB Ansatz implemented in TurboRVB has a large variational freedom, including the Jastrow correlated Slater determinant as its simplest, but nontrivial case. Moreover, it has the remarkable advantage of remaining with an affordable computational cost, proportional to the one spent for the evaluation of a single Slater determinant. Therefore, its application to large systems is computationally feasible. The WF is expanded in a localized basis set. Several basis set functions are implemented, such as Gaussian, Slater, and mixed types, with no restriction on the choice of their contraction. The code implements the adjoint algorithmic differentiation that enables a very efficient evaluation of energy derivatives, comprising the ionic forces. Thus, one can perform structural optimizations and molecular dynamics in the canonical NVT ensemble at the VMC level. For the electronic part, a full WF optimization (Jastrow and antisymmetric parts together) is made possible, thanks to state-of-the-art stochastic algorithms for energy minimization. In the optimization procedure, the first guess can be obtained at the mean-field level by a built-in DFT driver. The code has been efficiently parallelized by using a hybrid MPI-OpenMP protocol, which is also an ideal environment for exploiting the computational power of modern Graphics Processing Unit accelerators. [ABSTRACT FROM AUTHOR]

In the present work, we apply recently developed real-time descriptors to study the time evolution of plasmonic features of pentagonal Ag clusters. The method is based on the propagation of the time-dependent Schrödinger equation within a singly excited TDDFT ansatz. We use transition contribution maps (TCMs) and induced density to characterize the optical longitudinal and transverse response of such clusters, when interacting with pulses resonant with the low-energy (around 2–3 eV, A 1 ) size-dependent or the high-energy (around 4 eV, E 1 ) size-independent peak. TCMs plots on the analyzed clusters, Ag 25 + and Ag 43 + show off-diagonal peaks consistent with a plasmonic response when a longitudinal pulse resonant at A 1 frequency is applied, and dominant diagonal spots, typical of a molecular transition, when a transverse E 1 pulse is employed. Induced densities confirm this behavior, with a dipole-like charge distribution in the first case. The optical features show a time delay with respect to the evolution of the external pulse, consistent with those found in the literature for real-time TDDFT calculations on metal clusters. [ABSTRACT FROM AUTHOR]

The interpretation of nanoplasmonic effects on molecular properties, such as metal-enhanced absorption or fluorescence, typically assumes a fully coherent picture (in the quantum-mechanical sense) of the phenomena. Yet, there may be conditions where the coherent picture breaks down, and the decoherence effect should be accounted for. Using a state-of-the-art multiscale model approach able to include environment-induced dephasing, here we show that metal nanoparticle effects on the light absorption by a nearby molecule is strongly affected (even qualitatively, i.e., suppression vs enhancement) by molecular electronic decoherence. The present work shows that decoherence can be thought of as a further design element of molecular nanoplasmonic systems. [ABSTRACT FROM AUTHOR]

Pathogenic variants in RASA1 are typically associated with a clinical condition called "capillary malformation-arteriovenous malformation" (CM-AVM) syndrome, an autosomal dominant genetic disease characterized by a broad phenotypic variability, even within families. In CM-AVM syndrome, multifocal capillary and arteriovenous malformations are mainly localized in the central nervous system, spine and skin. Although CM-AVM syndrome has been widely described in the literature, only 21 cases with prenatal onset of clinical features have been reported thus far. Here, we report four pediatric cases of molecularly confirmed CM-AVM syndrome which manifested during the prenatal period. Polyhydramnios, non-immune hydrops fetalis and chylothorax are only a few possible aspects of this condition, but a correct interpretation of these prenatal signs is essential due to the possible fatal consequences of unrecognized encephalic and thoracoabdominal deep vascular malformations in newborns and in family members carrying the same RASA1 variant. [ABSTRACT FROM AUTHOR]

Copyright of Arte & Ensaio is the property of Arte & Ensaio and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Revealing possible long-living coherence in ultrafast processes allows detecting genuine quantum mechanical effects in molecules. To investigate such effects from a quantum chemistry perspective, we have developed a method for simulating the time evolution of molecular systems based on ab initio calculations, which includes relaxation and environment-induced dephasing of the molecular wave function whose rates are external parameters. The proposed approach combines a quantum chemistry description of the molecular target with a real-time propagation scheme within the time-dependent stochastic Schrödinger equation. Moreover, it allows a quantitative characterization of the state and dynamics coherence through the l1-norm of coherence and the linear entropy, respectively. To test the approach, we have simulated femtosecond pulse-shaping ultrafast spectroscopy of terrylenediimide, a well-studied fluorophore in single-molecule spectroscopy. Our approach is able to reproduce the experimental findings [R. Hildner et al., Nat. Phys. 7, 172 (2011)], confirming the usefulness of the approach and the correctness of the implementation. [ABSTRACT FROM AUTHOR]

In this work, we present the computed high-harmonic generation (HHG) spectra of uracil and thymine molecules, by means of the real-time time-dependent formulation of Gaussian-based configuration interaction with single excitations (RT-TD-CIS). According to the experimental work [Hutchison et al., Comparison of high-order harmonic generation in uracil and thymine ablation plumes, Phys. Chem. Chem. Phys., 2013, 15, 12308], a pulse wavelength of 780 nm has been used, together with an intensity of 1014 W cm−2 and a pulse duration of 23 optical cycles. In order to examine the effect of pulse polarisation, rotationally averaged (to mimic the gas-phase sample) and single-polarisations have been computed for both molecules. Our results show that the HHG signal for both molecules possibly originates from different ionisation channels, involving HOMO, HOMO−1, HOMO−2 and HOMO−3 orbitals, which lie within 4 eV. We characterize the HHG spectrum of thymine, supporting the idea that the absence of the thymine signal in the original work does not depend on the single-molecule behaviour. Present results for uracil are consistent with the experimental data. Moreover, we have observed that states below and above the chosen ionisation threshold provide different contributions to the HHG spectrum in averaged and single-polarisation calculations. [ABSTRACT FROM AUTHOR]

The article informs that alternative to the opposition between the city and the forest, between civilization and the wild can be found. It mentions that Carolyn Steel's studies have shown that the image of the city as a geographic space, physically inhabited and occupied by a community of citizens, is an illusion.

Ultrafast two-pulse experiments on single molecules are invaluable tools to investigate the microscopic dynamics of a fluorophore. The first pulse generates electronic or vibronic coherence and the second pulse probes the time-evolution of the coherence. A protocol that is able to simulate ultrafast experiments on single molecules is applied in this study. It is based on a coupled quantum-mechanical description of the fluorophore and real-time dynamics of the system vibronic wave packet interacting with an electric field, described by means of the stochastic Schrödinger equation within the Markovian limit. This approach is applied to the DNQDI fluorophore, previously investigated experimentally [D. Brinks et al., Nature, 2010, 465, 905–908]. We find this to be in good agreement with the experimental outcomes and provide microscopic and atomistic interpretation. [ABSTRACT FROM AUTHOR]

We report an extension of diffusion Monte Carlo (DMC) to the calculation of the molecular rotational energies by means of the generalized, symmetry-adapted, imaginary-time correlation functions (SAITCFs) originally introduced in the reptation quantum Monte Carlo (RQMC) framework (Škrbić in J Phys Chem A 111:12749, 2007). We studied the a-type and b-type rotational lines of the CO( $$^{4}$$ He) $$_{N}$$ clusters with $$N=$$ 1-8 that correlate, in the dimer limit, with the end-over-end and free-rotor transitions. We compare the SAITCF-DMC results with accurate DVR (for the dimer case), RQMC and other DMC data, and with reference experimental findings (Surin in Phys Rev Lett 101:233401, 2008). A good agreement is generally found, but a systematic underestimation of the SAITCF-DMC rotational energies of the b-type series is observed. Sources of inaccuracy in our theoretical approach and in the computational protocol are discussed and analyzed in detail. [ABSTRACT FROM AUTHOR]

The computation of high-harmonic generation spectra by means of Gaussian basis sets in approaches propagating the time-dependent Schrödinger equation was explored. The efficiency of Gaussian functions specifically designed for the description of the continuum proposed by Kaufmann et al. (J Phys B 1989, 22, 2223) was investigated. The range of applicability of this approach was assessed by studying the hydrogen atom, that is, the simplest atom for which 'exact' calculations on a grid could be performed. The effect of increasing the basis set cardinal number, the number of diffuse basis functions, and the number of Gaussian pseudo-continuum basis functions for various laser parameters was notably studied. The results showed that the latter significantly improved the description of the low-lying continuum states, and provided a satisfactory agreement with grid calculations for laser wavelengths λ0 = 800 and 1064 nm. The Kaufmann continuum functions, therefore, appeared as a promising way of constructing Gaussian basis sets for studying molecular electron dynamics in strong laser fields using time-dependent quantum-chemistry approaches. © 2016 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

High-harmonic generation (HHG) is used to produce coherent XUV and soft X-ray radiation with attosecond resolution and is a sensitive tool for probing atomic and molecular structures. In this work, we have used time-dependent configuration interaction with a Gaussian basis set to compute the HHG spectrum of the hydrogen atom. To get a correct description of the HHG optical spectrum, the Gaussian basis set has to provide an accurate representation of the bound and the continuum states. Two strategies have been proposed: (1) multicentered (defining ghost atoms around the hydrogen) and (2) optimal-continuum Gaussian basis sets. We have systematically investigated these two approaches for the hydrogen atom, which permits a non-biased analysis of the basis set. Several basis sets have been constructed and tested by combining multicentered and optimal-continuum functions together in order to obtain a reliable and accurate Gaussian basis set to be used for HHG. We have studied the effect of changing the number of ghost atoms and the distance between the ghosts and the hydrogen atom, with and without optimal-continuum Gaussian functions. We conclude that multicentered basis sets are less efficient than basis sets using only optimal-continuum Gaussian functions for a proper description of HHG. [ABSTRACT FROM AUTHOR]

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In this work, we study the electronic and geometrical properties of the ground state of the Retinal Minimal Model C5H6NH2+ using the variational Monte Carlo (VMC) method by means of the Jastrow antisymmetrized geminal power (JAGP) wavefunction. A full optimization of all wavefunction parameters, including coefficients, and exponents of the atomic basis, has been achieved, giving converged geometries with a compact and correlated wavefunction. The relaxed geometries of the cis and trans isomers present a pronounced bond length alternation pattern characterized by a CC central double bond slightly shorter than that reported by the CASPT2 structures. The comparison between different basis sets indicates converged values of geometrical parameters, energy differences, and dipole moments even when the smallest wavefunction is used. The compactness of the wavefunction as well as the scalability of VMC optimization algorithms on massively parallel computers opens the way to perform full structural optimizations of conjugated biomolecules of hundreds of electrons by correlated methods like Quantum Monte Carlo. © 2012 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Copyright of Revue de Synthèse is the property of Brill Academic Publishers and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

We report a computational study at the time-dependent density functional theory (TDDFT) level of the chiro-optical spectra of chiral gold nanowires coupled in dimers. Our goal is to explore whether it is possible to overcome destructive interference in single nanowires that damp chiral response in these systems and to achieve intense plasmonic circular dichroism (CD) through a coupling between the nanostructures. We predict a huge enhancement of circular dichroism at the plasmon resonance when two chiral nanowires are intimately coupled in an achiral relative arrangement. Such an effect is even more pronounced when two chiral nanowires are coupled in a chiral relative arrangement. Individual component maps of rotator strength, partial contributions according to the magnetic dipole component, and induced densities allow us to fully rationalize these findings, thus opening the way to the field of plasmonic CD and its rational design. [ABSTRACT FROM AUTHOR]

Coupling the real-time description of the ultrafast electron dynamics in strong laser fields with quantum chemistry techniques still represents an open challenge for theoreticians. In this work, high-harmonic generation (HHG) spectrum of the argon atom has been computed by means of the time-dependent configuration with singly excited configurations approach (TDCIS), using Gaussian basis sets. We show that adding a number of continuum-optimal Gaussian functions to basis sets routinely used in quantum chemistry calculations provides the expected position of the intensity minimum in the HHG spectrum, for a given selection of laser intensities and ionisation parameters. Advantages and weaknesses of the proposed computational strategy are discussed. We give evidence here that Gaussian-based TDCIS simulations are accurate enough to correctly reproduce the features of ultrafast and highly nonlinear optical processes, as HHG. [ABSTRACT FROM AUTHOR]