Controlling Electronic Coherences and the Curvature Induced by the Derivative Coupling at a Conical Intersection: A Quantum Ehrenfest (QuEh) Protocol for Reaction Path Following Application to "Channel 3" Benzene Photochemistry.

We report a protocol for the implementation of "reaction path following" from a transition state through a conical intersection, including both the path curvature induced by the derivative coupling and the corresponding induced electronic coherences. This protocol focuses on the "central" Gaussian wavepacket (initially unexcited) in the quantum Ehrenfest (QuEh) method. Like the reaction path following, the normal mode corresponding to the imaginary frequency at the transition state is given an initial momentum. The protocol is applied to the "channel 3" radiationless decay of benzene. We also demonstrate that one can enhance the effect of the derivative coupling and the electronic coherence with an IR pulse.

Estimates of speech efficiency in monolingual and bilingual speakers of English.

Introduction The Speech Efficiency Score (SES) serves as an acoustic metric for assessing fluency in conversational speech within the temporal domain. This study leverages SES to investigate conversational speech efficiency among native speakers of American English (AE) compared to speakers of Mandarin-accented English (MAE). Methods SES, speaking rate, articulation rate, and vocabulary diversity were measured and compared between two groups: native AE speakers and MAE speakers. The study utilized conversational speech samples collected from both groups to analyze these metrics. Results Findings indicate a disparity in speaking rate and articulation rate between the AE and MAE groups, with the AE group exhibiting significantly faster speech. However, no significant differences were observed in SES and vocabulary diversity between the two groups. Conclusion The results are discussed in the context of the interplay between speaking rate, speech fluency, and vocabulary diversity. These findings shed light on the maintenance of speech efficiency among bilingual speakers, suggesting that despite differences in speaking rate and articulation rate, SES and vocabulary diversity remain comparable between native AE speakers and MAE speakers. .

How electronic superpositions drive nuclear motion following the creation of a localized hole in the glycine radical cation.

In this work, we have studied the nuclear and electron dynamics in the glycine cation starting from localized hole states using the quantum Ehrenfest method. The nuclear dynamics is controlled both by the initial gradient and by the instantaneous gradient that results from the oscillatory electron dynamics (charge migration). We have used the Fourier transform (FT) of the spin densities to identify the "normal modes" of the electron dynamics. We observe an isomorphic relationship between the electron dynamics normal modes and the nuclear dynamics, seen in the vibrational normal modes. The FT spectra obtained this way show bands that are characteristic of the energy differences between the adiabatic hole states. These bands contain individual peaks that are in one-to-one correspondence with atom pair (+·) ↔ (·+) resonances, which, in turn, stimulate nuclear motion involving the atom pair. With such understanding, we anticipate "designer" coherent superpositions that can drive nuclear motion in a particular direction.

Properties of Relative Timing and Phonetic Complexity in Adults with Dysarthria Secondary to Amyotrophic Lateral Sclerosis.

INTRODUCTION: This study examined the relative timing in individuals with dysarthria secondary to amyotrophic lateral sclerosis (ALS). The aim was to examine whether the relative timing was influenced by severity of dysarthria and phonetic complexity of the speech being produced. METHODS: Twenty-one adults with dysarthria secondary to ALS, who presented with a range of dysarthria severity, participated in the study. A group of nonimpaired, age-matched adults served as controls. All participants produced a single phrase, across which four measures of relative timing were calculated, and the phonetic composition (complexity) of each measure was considered. Both participant groups completed the Sentence Intelligibility Test, which provided measures of speech intelligibility and speaking rate. RESULTS: Relative timing did not significantly differ between speaker groups across the four measures, regardless of phonetic complexity. Neither Sentence Intelligibility Test score nor speaking rate were significantly correlated with relative timing. DISCUSSION: Relative timing of phrase-level speech appears to remain intact regardless of the phonetic complexity of speech among individuals with dysarthria secondary to ALS. The potential of an internal phonological system organizing speech gestures is discussed to explain why the consistency in relative timing occurs.

Differential stuttering during conversation and oral reading in Kuwaiti-Arabic speakers: a note on diglossia.

The current study aimed to explore the frequency and types of stuttering in the oral reading and conversational samples of Arabic adults who stutter (AWS). Twelve Kuwaiti-Arabic AWS (mean age: 27.3 years) participated in the study. Each participant's stuttering was analyzed in two speaking contexts -oral reading of a standard Arabic passage and spontaneous conversational speech. The results showed that among a majority of the participants the amount of stuttering in conversation was significantly lower than that of reading. However, no significant differences were found in disfluency types within and between samples. The higher occurrence of stuttering in reading may be related to the diglossic nature of Arabic. The linguistic and rhythmic distinctions between Modern Standard Arabic (MSA) and Kuwaiti dialectal Arabic are explored to further explain the findings.

Disfluency characteristics of Omani Arabic-English bilingual speakers.

This study examined the oral reading and conversational speech of eight bilinguals who stutter (BWS). The participants spoke Omani Arabic as the dominant and English as the less-dominant language. The samples were examined with particular reference to the production of overall disfluency, stuttering-like disfluencies (SLDs) and other-disfluencies (ODs) occurring at the syllable and word level. The results indicated no difference in the amount of overall disfluency or ODs between the two languages in either reading or conversation. A significantly higher amount of SLDs were found to occur in words during reading in Arabic compared to English, which was attributed to the linguistic complexity of formal Arabic. A higher amount of SLDs in syllables were found in English compared to Arabic during conversation, although no such difference was found at the word level. The results align with a small body of research suggesting equivalent amounts of stuttering between dominant and less-dominant languages during conversation. The finding of a higher amount of stuttering during reading in Arabic is suggestive of motor differences in the production of the two languages that differentially affect speech fluency.

Multifaceted highly targeted sequential multidrug treatment of early ambulatory high-risk SARS-CoV-2 infection (COVID-19).

The SARS-CoV-2 virus spreading across the world has led to surges of COVID-19 illness, hospitalizations, and death. The complex and multifaceted pathophysiology of life-threatening COVID-19 illness including viral mediated organ damage, cytokine storm, and thrombosis warrants early interventions to address all components of the devastating illness. In countries where therapeutic nihilism is prevalent, patients endure escalating symptoms and without early treatment can succumb to delayed in-hospital care and death. Prompt early initiation of sequenced multidrug therapy (SMDT) is a widely and currently available solution to stem the tide of hospitalizations and death. A multipronged therapeutic approach includes 1) adjuvant nutraceuticals, 2) combination intracellular anti-infective therapy, 3) inhaled/oral corticosteroids, 4) antiplatelet agents/anticoagulants, 5) supportive care including supplemental oxygen, monitoring, and telemedicine. Randomized trials of individual, novel oral therapies have not delivered tools for physicians to combat the pandemic in practice. No single therapeutic option thus far has been entirely effective and therefore a combination is required at this time. An urgent immediate pivot from single drug to SMDT regimens should be employed as a critical strategy to deal with the large numbers of acute COVID-19 patients with the aim of reducing the intensity and duration of symptoms and avoiding hospitalization and death.

The quantum-Ehrenfest method with the inclusion of an IR pulse: Application to electron dynamics of the allene radical cation.

We describe the implementation of a laser control pulse in the quantum-Ehrenfest method, a molecular quantum dynamics method that solves the time-dependent Schrödinger equation for both electrons and nuclei. The oscillating electric field-dipole interaction is incorporated directly in the one-electron Hamiltonian of the electronic structure part of the algorithm. We then use the coupled electron-nuclear dynamics of the π-system in the allene radical cation (•CH2=C=CH2)+ as a simple model of a pump-control experiment. We start (pump) with a two-state superposition of two cationic states. The resulting electron dynamics corresponds to the rapid oscillation of the unpaired electron between the two terminal methylenes. This electron dynamics is, in turn, coupled to the torsional motion of the terminal methylenes. There is a conical intersection at 90° twist, where the electron dynamics collapses because the adiabatic states become degenerate. After passing the conical intersection, the electron dynamics revives. The IR pulse (control) in our simulations is timed to have its maximum at the conical intersection. Our simulations show that the effect of the (control) pulse is to change the electron dynamics at the conical intersection and, as a consequence, the concomitant nuclear dynamics, which is dominated by the change in the torsional angle.

Estimates of functional cerebral hemispheric differences in monolingual and bilingual people who stutter: dichotic listening paradigm.

Recent studies indicate functional cerebral hemispheric processing differences between monolinguals and bilinguals who stutter, as well as monolinguals and bilinguals who do not stutter. Eighty native German speakers, half of whom were also proficient speakers of English as a second language (L2), were assessed on a dichotic listening paradigm using CV syllables as stimuli. The participants were organised into four different groups according to speech status and language ability: 20 monolinguals who stutter, 20 bilinguals who stutter, 20 monolinguals who do not stutter, and 20 bilinguals who do not stutter. A right ear advantage (REA) was observed across all groups with no significant group differences in regard to hemispheric asymmetry. Although MWS (18 dB) and BWS (16 dB) crossed over to an LEA at an earlier point compared to the MWNS (5 dB) and BWNS (2 dB), the difference between groups was minor and not significant. Thus, a significant difference in REA resistance, as proposed by other researchers, was not reflected in the current study neither for people who stutter nor for bilinguals. In addition, no meaningful relationship was found between dichotic listening and stuttering severity, as well as the four language modalities (listening, speaking, reading, writing). Thus, we contend that neither stuttering nor bilingualism has any non-trivial effect on functional cerebral hemispheric differences in language processing in dichotic listening.

Molecular Vertical Excitation Energies Studied with First-Order RASSCF (RAS[1,1]): Balancing Covalent and Ionic Excited States.

RASSCF calculations of vertical excitation energies were carried out on a benchmark set of 19 organic molecules studied by Thiel and co-workers [ J. Chem. Phys. 2008 , 128 , 134110 ]. The best results, in comparison with the MS-CASPT2 results of Thiel, were obtained using a RASSCF space that contains at most one hole and one particle in the RAS1 and RAS3 spaces, respectively, which we denote as RAS[1,1]. This subset of configurations recovers mainly the effect of polarization and semi-internal electronic correlation that is only included in CASSCF in an averaged way. Adding all-external correlation by allowing double excitations from RAS1 and RAS2 into RAS3 did not improve the results, and indeed, they were slightly worse. The accuracy of the first-order RASSCF computations is demonstrated to be a function of whether the state of interest can be classified as covalent or ionic in the space of configurations built from orbitals localized onto atomic sites. For covalent states, polarization and semi-internal correlation effects are negligible (RAS[1,1]), while for ionic states, these effects are large (because of inherent diffusiveness of these states compared to the covalent states) and, thus, an acceptable agreement with MS-CASPT2 can be obtained using first-order RASSCF with the extra basis set involving 3p orbitals in most cases. However, for those ionic states that are quasi-degenerate with a Rydberg state or for nonlocal nπ* states, there remains a significant error resulting from all external correlation effects.

Curve crossing in a manifold of coupled electronic states: direct quantum dynamics simulations of formamide.

Quantum dynamics simulations are an important tool to evaluate molecular behaviour including the, often key, quantum nature of the system. In this paper we present an algorithm that is able to simulate the time evolution of a molecule after photo-excitation into a manifold of states. The direct dynamics variational multi-configurational Gaussian (DD-vMCG) method circumvents the computational bottleneck problems of traditional grid-based methods by computing the potential energy functions on-the-fly, i.e. only where required. Unlike other commonly used direct dynamics methods, DD-vMCG is fully quantum mechanical. Here, the method is combined with a novel on-the-fly diabatisation scheme to simulate the short-time dynamics of the key molecule formamide and its acid analogue formimidic acid. This is a challenging test system due to the nature and large number of excited states, and eight coupled states are included in the calculations. It is shown that the method is able to provide unbiased information on the product channels open after excitation at different energies and demonstrates the potential to be a practical scheme, limited mainly by the quality of the quantum chemistry used to describe the excited states.

A Definition of the Magnetic Transition Temperature Using Valence Bond Theory.

Macroscopic magnetic properties are analyzed using Valence Bond theory. Commonly the critical temperature TC for magnetic systems is associated with a maximum in the energy-based heat capacity Cp(T). Here a more broadly applicable definition of the magnetic transition temperature TC is described using the spin moment expectation value (i.e., applying the spin exchange density operator) instead of energy. Namely, the magnetic capacity Cs(T) reflects variation in the spin multiplicity as a function of temperature, which is shown to be related to ∂[χT(T)]/∂T. Magnetic capacity Cs(T) depends on long-range spin interactions that are not relevant in the energy-based heat capacity Cp(T). Differences between Cs(T) and Cp(T) are shown to be due to spin order/disorder within the crystal that can be monitored via a Valence Bond analysis of the corresponding magnetic wave function. Indeed the concept of the Boltzmann spin-alignment order is used to provide information about the spin correlation between magnetic units. As a final illustration, the critical temperature is derived from the magnetic capacity for several molecular magnets presenting different magnetic topologies that have been experimentally studied. A systematic shift between the transition temperatures associated with Cs(T) and Cp(T) is observed. It is demonstrated that this shift can be attributed to the loss of long-range spin correlation. This suggests that the magnetic capacity Cs(T) can be used as a predictive tool for the magnetic topology and thus for the synthetic chemists.

The Ehrenfest method with fully quantum nuclear motion (Qu-Eh): Application to charge migration in radical cations.

An algorithm is described for quantum dynamics where an Ehrenfest potential is combined with fully quantum nuclear motion (Quantum-Ehrenfest, Qu-Eh). The method is related to the single-set variational multi-configuration Gaussian approach (vMCG) but has the advantage that only a single quantum chemistry computation is required at each time step since there is only a single time-dependent potential surface. Also shown is the close relationship to the "exact factorization method." The quantum Ehrenfest method is compared with vMCG for study of electron dynamics in a modified bismethylene-adamantane cation system. Illustrative examples of electron-nuclear dynamics are presented for a distorted allene system and for HCCI+ where one has a degenerate Π system.

Electron Dynamics upon Ionization of Polyatomic Molecules: Coupling to Quantum Nuclear Motion and Decoherence.

Knowledge about the electronic motion in molecules is essential for our understanding of chemical reactions and biological processes. The advent of attosecond techniques opens up the possibility to induce electronic motion, observe it in real time, and potentially steer it. A fundamental question remains the factors influencing electronic decoherence and the role played by nuclear motion in this process. Here, we simulate the dynamics upon ionization of the polyatomic molecules paraxylene and modified bismethylene-adamantane, with a quantum mechanical treatment of both electron and nuclear dynamics using the direct dynamics variational multiconfigurational Gaussian method. Our simulations give new important physical insights about the expected decoherence process. We have shown that the decoherence of electron dynamics happens on the time scale of a few femtoseconds, with the interplay of different mechanisms: the dephasing is responsible for the fast decoherence while the nuclear overlap decay may actually help maintain it and is responsible for small revivals.

Estimates of functional cerebral hemispheric differences in monolingual and bilingual people who stutter: Visual hemifield paradigm.

The relationship between stuttering and bilingualism to functional cerebral hemispheric processing was examined using a visual hemifield paradigm. Eighty native German speakers, half of whom were also proficient speakers of English as a second language (L2), were recruited. The participants were organised into four different groups according to speech status and language ability: 20 monolinguals who stutter, 20 bilinguals who stutter, 20 monolinguals who do not stutter, and 20 bilinguals who do not stutter. All participants completed a task involving selective identification of common objects simultaneously presented to both visual fields. Overall, an LVF advantage was observed across all groups with no significant group differences in regard to hemispheric asymmetry. However, both bilingual groups showed faster reaction times and fewer identification errors than the two monolingual groups. A prevailing finding was that bilingualism seems to offset deficits in executive functioning associated with stuttering. Hence, the results lend support to previous findings implicating the benefits of bilingualism.

Estimates of functional cerebral hemispheric differences in monolingual and bilingual people who stutter: Dual-task paradigm.

The inter-relationship of stuttering and bilingualism to functional cerebral hemispheric processing was examined on a dual-task paradigm. Eighty native German (L1) speakers, half of whom were sequential bilinguals (L2 = English), were recruited. The participants (mean age = 38.9 years) were organised into four different groups according to speech status and language ability: 20 bilinguals who stutter (BWS), 20 monolinguals who stutter (MWS), 20 bilinguals who do not stutter (BWNS), and 20 monolinguals who do not stutter (MWNS). All participants completed a dual-task paradigm involving simultaneous speaking and finger tapping. No performance differences between BWS and BWNS were found. In contrast, MWS showed greater dual-task interference compared to BWS and MWNS, as well as greater right- than left-hand disruption. A prevailing finding was that bilingualism seems to offset deficits in executive functioning associated with stuttering. Cognitive reserve may have been reflected in the present study, resulting in a bilingual advantage.

Electron and nuclear dynamics following ionisation of modified bismethylene-adamantane.

We have simulated the coupled electron and nuclear dynamics using the Ehrenfest method upon valence ionisation of modified bismethylene-adamantane (BMA) molecules where there is an electron transfer between the two π bonds. We have shown that the nuclear motion significantly affects the electron dynamics after a few fs when the electronic states involved are close in energy. We have also demonstrated how the non-stationary electronic wave packet determines the nuclear motion, more precisely the asymmetric stretching of the two π bonds, illustrating "charge-directed reactivity". Taking into account the nuclear wave packet width results in the dephasing of electron dynamics with a half-life of 8 fs; this eventually leads to the equal delocalisation of the hole density over the two methylene groups and thus symmetric bond lengths.

Nuclear spatial delocalization silences electron density oscillations in 2-phenyl-ethyl-amine (PEA) and 2-phenylethyl-N,N-dimethylamine (PENNA) cations.

We simulate electron dynamics following ionization in 2-phenyl-ethyl-amine and 2-phenylethyl-N,N-dimethylamine as examples of systems where 3 coupled cationic states are involved. We study two nuclear effects on electron dynamics: (i) coupled electron-nuclear motion and (ii) nuclear spatial delocalization as a result of the zero-point energy in the neutral molecule. Within the Ehrenfest approximation, our calculations show that the coherent electron dynamics in these molecules is not lost as a result of coupled electron-nuclear motion. In contrast, as a result of nuclear spatial delocalization, dephasing of the oscillations occurs on a time scale of only a few fs, long before any significant nuclear motion can occur. The results have been rationalized using a semi-quantitative model based upon the gradients of the potential energy surfaces.

Charge migration in polycyclic norbornadiene cations: Winning the race against decoherence.

The observation of electronic motion remains a key target in the development of the field of attoscience. However, systems in which long-lived oscillatory charge migration may be observed must be selected carefully, particularly because it has been shown that nuclear spatial delocalization leads to a loss of coherent electron density oscillations. Here we demonstrate electron dynamics in norbornadiene and extended systems where the hole density migrates between two identical chromophores. By studying the effect of nuclear motion and delocalization in these example systems, we present the physical properties that must be considered in candidate molecules in which to observe electron dynamics. Furthermore, we also show a key contribution to nuclear delocalization arises from motion in the branching plane of the cation. For the systems studied, the dephasing time increases with system size while the energy gap between states, and therefore the frequency of the density oscillation, decreases with size (obeying a simple exponential dependence on the inter-chromophore distance). We present a system that balances these two effects and shows several complete oscillations in the spin density before dephasing occurs.

Communication restriction in adults who stutter: Part II.

This article presents a follow-up study to Lee, van Dulm, Robb, and Ormond (2015). The aim was to explore communication restriction in adults with stuttering (AWS) using typical language measures and systemic functional linguistics (SFL) analyses. The article compared the pre- and post-treatment performance of AWS in language productivity and complexity, transitivity, modality, appraisal, and theme. Ten-minute conversational samples were obtained from 20 AWS before and after participation in intensive stuttering treatment. Transcripts were analysed for quantity and complexity of verbal output, and frequency of transitivity, modality, appraisal and theme resources. Between pre- and post-treatment, the following differences were observed: (1) a significant increase in frequency of modal operators, and trends approaching significance for (2) increased language complexity (3) increased language expressing appraisal. These changes suggest increased flexibility of language use in AWS following treatment, particularly towards interpersonal engagement. The value of SFL to this area of research is discussed.