Scalable Ab Initio Electronic Structure Methods with Near Chemical Accuracy for Main Group Chemistry.

This study evaluates the precision of widely recognized quantum chemical methodologies, CCSD(T), DLPNO-CCSD(T), and localized ph-AFQMC, for determining the thermochemistry of main group elements. DLPNO-CCSD(T) and localized ph-AFQMC, which offer greater scalability compared to canonical CCSD(T), have emerged over the past decade as pivotal in producing precise benchmark chemical data. Our investigation includes closed-shell, neutral molecules, focusing on their heat of formation and atomization energy sourced from four specific small molecule data sets.

Evaluation of the Parkinson's Remote Interactive Monitoring System in a Clinical Setting: Usability Study.

Background: The fastest-growing neurological disorder is Parkinson disease (PD), a progressive neurodegenerative disease that affects 10 million people worldwide. PD is typically treated with levodopa, an oral pill taken to increase dopamine levels, and other dopaminergic agonists. As the disease advances, the efficacy of the drug diminishes, necessitating adjustments in treatment dosage according to the patient's symptoms and disease progression.

Performance Investigations of InAs/InP Quantum-Dash Semiconductor Optical Amplifiers with Different Numbers of Dash Layers.

We present here a performance comparison of quantum-dash (Qdash) semiconductor amplifiers (SOAs) with three, five, eight, and twelve InAs dash layers grown on InP substrates. Other than the number of Qdash layers, the structures were identical. The eight-layer Qdash SOA gave the highest amplified spontaneous emission power (4.

Expanding the Design Space of Constraints in Auxiliary-Field Quantum Monte Carlo.

We formulate and characterize a new constraint for auxiliary-field quantum Monte Carlo (AFQMC) applicable for general fermionic systems, which allows for the accumulation of phase in the random walk but disallows walkers with a magnitude of phase greater than π with respect to the trial wave function. For short imaginary times, before walkers accumulate sizable phase values, this approach is equivalent to exact free projection, allowing one to observe the accumulation of bias associated with the constraint and thus estimate its magnitude . We demonstrate the stability of this constraint over arbitrary imaginary times and system sizes, highlighting the removal of noise due to the fermionic sign problem.

Accurate Quantum Chemical Reaction Energies for Lithium-Mediated Electrolyte Decomposition and Evaluation of Density Functional Approximations.

An important concern related to the performance of Li-ion batteries is the formation of a solid electrolyte interphase on the surface of the anode. This film is formed from the decomposition of electrolytes and can have important effects on the stability and performance. Here, we evaluate the decomposition pathway of ethylene carbonate and related organic electrolyte molecules using a series of density functional approximations and correlated wave function (WF) methods, including the coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] and auxiliary-field quantum Monte Carlo (AFQMC).

Toward Benchmark-Quality Predictions for 3d Transition Metal Electrocatalysts: A Comparison of CCSD(T) and ph-AFQMC.

Generating accurate ionization energies for transition metal complexes is an important step toward the accurate computational description of their electrocatalytic reactions. Benchmark-quality data is required for testing existing theoretical methods and developing new ones but is complicated to obtain for many transition metal compounds due to the potential presence of both strong dynamical and static electron correlation. In this regime, it is questionable whether the so-called gold standard, coupled cluster with singles, doubles, and perturbative triples (CCSD(T)), provides the desired level of accuracy─roughly 1-3 kcal/mol.

On the potentially transformative role of auxiliary-field quantum Monte Carlo in quantum chemistry: A highly accurate method for transition metals and beyond.

Approximate solutions to the ab initio electronic structure problem have been a focus of theoretical and computational chemistry research for much of the past century, with the goal of predicting relevant energy differences to within "chemical accuracy" (1 kcal/mol). For small organic molecules, or in general, for weakly correlated main group chemistry, a hierarchy of single-reference wave function methods has been rigorously established, spanning perturbation theory and the coupled cluster (CC) formalism. For these systems, CC with singles, doubles, and perturbative triples is known to achieve chemical accuracy, albeit at O(N) computational cost.

Targeted activation in localized protein environments via deep red photoredox catalysis.

State-of-the-art photoactivation strategies in chemical biology provide spatiotemporal control and visualization of biological processes. However, using high-energy light (λ < 500 nm) for substrate or photocatalyst sensitization can lead to background activation of photoactive small-molecule probes and reduce its efficacy in complex biological environments. Here we describe the development of targeted aryl azide activation via deep red-light (λ = 660 nm) photoredox catalysis and its use in photocatalysed proximity labelling.

A Localized-Orbital Energy Evaluation for Auxiliary-Field Quantum Monte Carlo.

Phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) has recently emerged as a promising method for the production of benchmark-level simulations of medium- to large-sized molecules because of its accuracy and favorable polynomial scaling with system size. Unfortunately, the memory footprints of standard energy evaluation algorithms are nontrivial, which can significantly impact timings on graphical processing units (GPUs) where memory is limited. Previous attempts to reduce scaling by taking advantage of the low-rank structure of the Coulombic integrals have been successful but exhibit high prefactors, making their utility limited to very large systems.

Reconfigurable microwave photonic filter based on a quantum dash mode-locked laser.

We demonstrate a reconfigurable microwave photonic (MWP) filter using a quantum dash (QDash) mode-locked laser (MLL) that can generate an optical frequency comb (OFC) with ∼50 comb lines and a free spectral range of 25 GHz. Thanks to the large number of comb lines, the MWP filter responses can be easily programmed by tailoring the OFC spectrum. We implement MWP filter responses with Gaussian, sinc, flat-top, and multiple peaks, as well as demonstrate that tuning of the central frequency.

Optical fibre-based single photon source using InAsP quantum dot nanowires and gradient-index lens collection.

We present a compact, fibre-coupled single photon source using gradient-index (GRIN) lenses and an InAsP semiconductor quantum dot embedded within an InP photonic nanowire waveguide. A GRIN lens assembly is used to collect photons close to the tip of the nanowire, coupling the light immediately into a single mode optical fibre. The system provides a stable, high brightness source of fibre-coupled single photons.

prediction of annihilators for triplet-triplet annihilation upconversion auxiliary-field quantum Monte Carlo.

The energy of the lowest-lying triplet state (T1) relative to the ground and first-excited singlet states (S0, S1) plays a critical role in optical multiexcitonic processes of organic chromophores. Focusing on triplet-triplet annihilation (TTA) upconversion, the S0 to T1 energy gap, known as the triplet energy, is difficult to measure experimentally for most molecules of interest. predictions can provide a useful alternative, however low-scaling electronic structure methods such as the Kohn-Sham and time-dependent variants of Density Functional Theory (DFT) rely heavily on the fraction of exact exchange chosen for a given functional, and tend to be unreliable when strong electronic correlation is present.

Biogeographical patterns of amphibians and reptiles in the northernmost coastal montane complex of South America.

We examine, for the first time, biogeographic patterns in a series of tropical montane coastal systems in northern South America. We use amphibians and reptiles, which constitute the most critical communities based upon the prevalence of endemic taxa, to assess the region's biodiversity. The montane coastal system spans an east-west distance of 925 km.

Molecular Engineering of Chromophores to Enable Triplet-Triplet Annihilation Upconversion.

Triplet-triplet annihilation upconversion (TTA-UC) is an unconventional photophysical process that yields high-energy photons from low-energy incident light and offers pathways for innovation across many technologies, including solar energy harvesting, photochemistry, and optogenetics. Within aromatic organic chromophores, TTA-UC is achieved through several consecutive energy conversion events that ultimately fuse two triplet excitons into a singlet exciton. In chromophores where the singlet exciton is roughly isoergic with two triplet excitons, the limiting step is the triplet-triplet annihilation pathway, where the kinetics and yield depend sensitively on the energies of the lowest singlet and triplet excited states.

The Pathology of Parkinson's Disease and Potential Benefit of Dietary Polyphenols.

Parkinson's disease (PD) is a progressive neurodegenerative disorder that is characterized by a loss of dopaminergic neurons, leading to bradykinesia, rigidity, tremor at rest, and postural instability, as well as non-motor symptoms such as olfactory impairment, pain, autonomic dysfunction, impaired sleep, fatigue, and behavioral changes. The pathogenesis of PD is believed to involve oxidative stress, disruption to mitochondria, alterations to the protein α-synuclein, and neuroinflammatory processes. There is currently no cure for the disease.

Predicting Ligand-Dissociation Energies of 3d Coordination Complexes with Auxiliary-Field Quantum Monte Carlo.

Transition-metal complexes are ubiquitous in biology and chemical catalysis, yet they remain difficult to accurately describe with methods because of the presence of a large degree of dynamic electron correlation, and, in some cases, strong static correlation which results from a manifold of low-lying states. Progress has been hindered by a scarcity of high-quality gas-phase experimental data, while exact predictions are usually computationally unaffordable because of the large size of the relevant complexes. In this work, we present a data set of 34 tetrahedral, square planar, and octahedral 3d metal-containing complexes with gas-phase ligand-dissociation energies that have reported uncertainties of ≤2 kcal/mol.

Cannabis use in pregnancy and breastfeeding: The pharmacist's role.

Background: The recent legalization of cannabis use in Canada requires pharmacists to be able to support their patients with accurate knowledge of its known risks and benefits. Certain populations, such as pregnant and breastfeeding women and their developing children, may be at higher risk than other populations.

Methods: The authors independently searched the literature for clinical reports or reviews of the literature regarding the safety of cannabis use in pregnancy and breastfeeding using search terms such as and .

Accurate Quantum Chemical Calculation of Ionization Potentials: Validation of the DFT-LOC Approach via a Large Data Set Obtained from Experiments and Benchmark Quantum Chemical Calculations.

Density functional theory (DFT) is known to often fail when calculating thermodynamic values, such as ionization potentials (IPs), due to nondynamical error (i.e., the self-interaction term).

Binge drinking in male adolescent rats and its relationship to persistent behavioral impairments and elevated proinflammatory/proapoptotic proteins in the cerebellum.

Rationale: To demonstrate that repeated episodes of binge drinking during the adolescent period can lead to long-term deficits in motor function and memory in adulthood, and increase proteins in the brain involved with inflammation and apoptotic cell death.

Methods: Groups of early adolescent (PND 26) and periadolescent (PND 34) Sprague-Dawley rats were exposed to either ethanol or plain air through a vapor chamber apparatus for five consecutive days (2 h per day), achieving a blood ethanol concentration equivalent to 6-8 drinks in the treatment group. Subjects then underwent a series of behavioral tests designed to assess memory, anxiety regulation, and motor function.

Farmers' preferred tree species and their potential carbon stocks in southern Burkina Faso: Implications for biocarbon initiatives.

The success of terrestrial carbon sequestration projects for rural development in sub-Saharan Africa lies in the (i) involvement of local populations in the selection of woody species, which represent the biological assets they use to meet their daily needs, and (ii) information about the potential of these species to store carbon. Although the latter is a key prerequisite, there is very little information available. To help fill this gap, the present study was undertaken in four pilot villages (Kou, Dao, Vrassan and Cassou) in Ziro Province, south-central Burkina Faso.