Correction: Increasing ion yield circular dichroism in femtosecond photoionisation using optimal control theory.

Correction for 'Increasing ion yield circular dichroism in femtosecond photoionisation using optimal control theory' by Manel Mondelo-Martell et al., Phys. Chem. Chem. Phys., 2022, 24, 9286-9297, https://doi.org/10.1039/D1CP05239J.

Resource-Efficient Dissipative Entanglement of Two Trapped-Ion Qubits.

We demonstrate a simplified method for dissipative generation of an entangled state of two trapped-ion qubits. Our implementation produces its target state faster and with higher fidelity than previous demonstrations of dissipative entanglement generation and eliminates the need for auxiliary ions. The entangled singlet state is generated in ∼7 ms with a fidelity of 0.949(4). The dominant source of infidelity is photon scattering. We discuss this error source and strategies for its mitigation.

Increasing ion yield circular dichroism in femtosecond photoionisation using optimal control theory.

We investigate how optimal control theory can be used to improve Circular Dichroism (CD) signals for the A-band of fenchone measured via the photoionization yield upon further excitation. These transitions are electric dipole forbidden to first order, which translates into low population transfer to the excited state but allows for a clearer interplay between electric and magnetic transition dipole moments, which are of the same order of magnitude. Using a model including the electronic ground and excited A state as well as all permanent and transition multipole moments up to the electric quadrupole, we find that the absolute CD signal of randomly oriented molecules can be increased by a factor of 2.5 when using shaped laser pulses, with the anisotropy parameter g increasing from 0.06 to 1. We find that this effect is caused by the interference between the excitation pathways prompted by the different multipole moments of the molecule.

Light modulation ameliorates expression of circadian genes and disease progression in spinal muscular atrophy mice.

Physiology and behaviour are critically dependent on circadian regulation via a core set of clock genes, dysregulation of which leads to metabolic and sleep disturbances. Metabolic and sleep perturbations occur in spinal muscular atrophy (SMA), a neuromuscular disorder caused by loss of the survival motor neuron (SMN) protein and characterized by motor neuron loss and muscle atrophy. We therefore investigated the expression of circadian rhythm genes in various metabolic tissues and spinal cord of the Taiwanese Smn-/-;SMN2 SMA animal model. We demonstrate a dysregulated expression of the core clock genes (clock, ARNTL/Bmal1, Cry1/2, Per1/2) and clock output genes (Nr1d1 and Dbp) in SMA tissues during disease progression. We also uncover an age- and tissue-dependent diurnal expression of the Smn gene. Importantly, we observe molecular and phenotypic corrections in SMA mice following direct light modulation. Our study identifies a key relationship between an SMA pathology and peripheral core clock gene dysregulation, highlights the influence of SMN on peripheral circadian regulation and metabolism and has significant implications for the development of peripheral therapeutic approaches and clinical care management of SMA patients.

Quantum Control of Photoelectron Circular Dichroism.

We demonstrate coherent control over the photoelectron circular dichroism in randomly oriented chiral molecules, based on quantum interference between multiple photoionization pathways. To significantly enhance the chiral signature, we use a finite manifold of indistinguishable (1+1^{'}) resonantly enhanced multiphoton ionization pathways interfering at a common photoelectron energy but probing different intermediate states. We show that this coherent control mechanism maximizes the number of molecular states that constructively contribute to the dichroism at an optimal photoelectron energy and thus outperforms other schemes, including interference between opposite-parity pathways driven by bichromatic (ω, 2ω) fields as well as sequential pump-probe ionization.

Perfect control of photoelectron anisotropy for randomly oriented ensembles of molecules by XUV REMPI and polarization shaping.

We report two schemes to generate perfect anisotropy in the photoelectron angular distribution of a randomly oriented ensemble of polyatomic molecules. In order to exert full control over the anisotropy of photoelectron emission, we exploit interferences between single-photon pathways and a manifold of resonantly enhanced two-photon pathways. These are shown to outperform nonsequential (ω, 2ω) bichromatic phase control for the example of CHFClBr molecules. We are able to optimize pulses that yield anisotropic photoelectron emission thanks to a very efficient calculation of photoelectron momentum distributions. This is accomplished by combining elements of quantum chemistry, variational scattering theory, and time-dependent perturbation theory.

Principles of enantio-selective excitation in three-wave mixing spectroscopy of chiral molecules.

Three-wave mixing spectroscopy of chiral molecules, which exist in left-handed and right-handed conformations, allows for enantioselective population transfer despite random orientation of the molecules. This is based on constructive interference of the three-photon pathways for one enantiomer and the destructive one for the other. We prove here that three mutually orthogonal polarization directions are required to this end. Two different dynamical regimes exist to realize enantioselective population transfer, and we show that they correspond to different phase conditions in the three-wave mixing. We find the excitation scheme used in current rotational three-wave mixing experiments of chiral molecules with C1 symmetry to be close to optimal and discuss the prospects for rovibrational three-wave mixing experiments of axially chiral molecules. Our comprehensive study allows us to clarify earlier misconceptions in the literature.

Photoassociation Spectroscopy in Penning Ionization Reactions at Sub-Kelvin Temperatures.

Penning ionization reactions in merged beams with precisely controlled collision energies have been shown to accurately probe quantum mechanical effects in reactive collisions. A complete microscopic understanding of the reaction is, however, faced with two major challenges-the highly excited character of the reaction's entrance channel and the limited precision of even the best state-of-the-art ab initio potential energy surfaces. Here, we suggest photoassociation spectroscopy as a tool to identify the character of orbiting resonances in the entrance channel and probe the ionization width as a function of interparticle separation. We introduce the basic concept, using the example of metastable helium and argon, and discuss the general conditions under which this type of spectroscopy will be successful.

Setting Priorities for Monitoring and Managing Non-native Plants: Toward a Practical Approach.

Land managers face the challenge to set priorities in monitoring and managing non-native plant species, as resources are limited and not all non-natives become invasive. Existing frameworks that have been proposed to rank non-native species require extensive information on their distribution, abundance, and impact. This information is difficult to obtain and often not available for many species and regions. National watch or priority lists are helpful, but it is questionable whether they provide sufficient information for environmental management on a regional scale. We therefore propose a decision tree that ranks species based on more simple albeit robust information, but still provides reliable management recommendations. To test the decision tree, we collected and evaluated distribution data from non-native plants in highland grasslands of Southern Brazil. We compared the results with a national list from the Brazilian Invasive Species Database for the state to discuss advantages and disadvantages of the different approaches on a regional scale. Out of 38 non-native species found, only four were also present on the national list. If management would solely rely on this list, many species that were identified as spreading based on the decision tree would go unnoticed. With the suggested scheme, it is possible to assign species to active management, to monitoring, or further evaluation. While national lists are certainly important, management on a regional scale should employ additional tools that adequately consider the actual risk of non-natives to become invasive.

Coherent Control of Bond Making.

We demonstrate coherent control of bond making, a milestone on the way to coherent control of photoinduced bimolecular chemical reactions. In strong-field multiphoton femtosecond photoassociation experiments, we find the yield of detected magnesium dimer molecules to be enhanced for positively chirped pulses and suppressed for negatively chirped pulses. Our ab initio model shows that control is achieved by purification combined with chirp-dependent Raman transitions. Experimental closed-loop phase optimization using a learning algorithm yields an improved pulse that utilizes vibrational coherent dynamics in addition to chirp-dependent Raman transitions. Our results show that coherent control of binary photoreactions is feasible even under thermal conditions.

Controlling magnetic Feshbach resonances in polar open-shell molecules with nonresonant light.

Magnetically tunable Feshbach resonances for polar paramagnetic ground-state diatomics are too narrow to allow for magnetoassociation starting from trapped, ultracold atoms. We show that nonresonant light can be used to engineer the Feshbach resonances in their position and width. For nonresonant field intensities of the order of 10(9) W/cm(2), we find the width to be increased by 3 orders of magnitude, reaching a few Gauss. This opens the way for producing ultracold molecules with sizable electric and magnetic dipole moments and thus for many-body quantum simulations with such particles.

Improving potential energy surfaces using measured Feshbach resonance states.

The structure and dynamics of a molecular system is governed by its potential energy surface (PES), representing the total energy as a function of the nuclear coordinates. Obtaining accurate potential energy surfaces is limited by the exponential scaling of Hilbert space, restricting quantitative predictions of experimental observables from first principles to small molecules with just a few electrons. Here, we present an explicitly physics-informed approach for improving and assessing the quality of families of PESs by modifying them through linear coordinate transformations based on experimental data. We demonstrate this "morphing" of the PES for the He - H2+ complex using recent comprehensive Feshbach resonance (FR) measurements for reference PESs at three different levels of quantum chemistry. In all cases, the positions and intensities of peaks in the energy distributions are improved. We find these observables to be mainly sensitive to the long-range part of the PES.

Optimal strategies for estimating the average fidelity of quantum gates.

We show that the minimum experimental effort to estimate the average error of a quantum gate scales as 2(n) for n qubits and requires classical computational resources ∼n(2)2(3n) when no specific assumptions on the gate can be made. This represents a reduction by 2(n) compared to the best currently available protocol, Monte Carlo characterization. The reduction comes at the price of either having to prepare entangled input states or obtaining bounds rather than the average fidelity itself. It is achieved by applying Monte Carlo sampling to so-called 2-designs or two classical fidelities. For the specific case of Clifford gates, the original version of Monte Carlo characterization based on the channel-state isomorphism remains an optimal choice. We provide a classification of the available efficient strategies to determine the average gate error in terms of the number of required experimental settings, average number of actual measurements, and classical computational resources.

The dietary flavonoids naringenin and quercetin acutely impair glucose metabolism in rodents possibly via inhibition of hypothalamic insulin signalling.

Secondary metabolites of herbs and spices are widely used as an alternative strategy in the therapy of various diseases. The polyphenols naringenin, quercetin and curcumin have been characterised as anti-diabetic agents. Conversely, in vitro, naringenin and quercetin are described to inhibit phosphoinositide-3-kinase (PI3K), an enzyme that is essential for the neuronal control of whole body glucose homoeostasis. Using both in vitro and in vivo experiments, we tested whether the inhibitory effect on PI3K occurs in neurons and if it might affect whole body glucose homoeostasis. Quercetin was found to inhibit basal and insulin-induced phosphorylation of Akt (Ser473), a downstream target of PI3K, in HT-22 cells, whereas naringenin and curcumin had no effect. In Djungarian hamsters (Phodopus sungorus) naringenin and quercetin (10 mg/kg administered orally) diminished insulin-induced phosphorylation of Akt (Ser473) in the arcuate nucleus, indicating a reduction in hypothalamic PI3K activity. In agreement with this finding, glucose tolerance in naringenin-treated hamsters (oral) and mice (oral and intracerebroventricular) was reduced compared with controls. Dietary quercetin also impaired glucose tolerance, whereas curcumin was ineffective. Circulating levels of insulin and insulin-like growth factor-binding protein were not affected by the polyphenols. Oral quercetin reduced the respiratory quotient, suggesting that glucose utilisation was impaired after treatment. These data demonstrate that low doses of naringenin and quercetin acutely and potently impair glucose homoeostasis. This effect may be mediated by inhibition of hypothalamic PI3K signalling. Whether chronic impairments in glucose homoeostasis occur after long-term application remains to be identified.

Femtosecond two-photon photoassociation of hot magnesium atoms: a quantum dynamical study using thermal random phase wavefunctions.

Two-photon photoassociation of hot magnesium atoms by femtosecond laser pulses, creating electronically excited magnesium dimer molecules, is studied from first principles, combining ab initio quantum chemistry and molecular quantum dynamics. This theoretical framework allows for rationalizing the generation of molecular rovibrational coherence from thermally hot atoms [L. Rybak, S. Amaran, L. Levin, M. Tomza, R. Moszynski, R. Kosloff, C. P. Koch, and Z. Amitay, Phys. Rev. Lett. 107, 273001 (2011)]. Random phase thermal wavefunctions are employed to model the thermal ensemble of hot colliding atoms. Comparing two different choices of basis functions, random phase wavefunctions built from eigenstates are found to have the fastest convergence for the photoassociation yield. The interaction of the colliding atoms with a femtosecond laser pulse is modeled non-perturbatively to account for strong-field effects.

Hypothalamic glycogen synthase kinase 3ß has a central role in the regulation of food intake and glucose metabolism.

GSK3ß (glycogen synthase kinase 3ß) is a ubiquitous kinase that plays a key role in multiple intracellular signalling pathways, and increased GSK3ß activity is implicated in disorders ranging from cancer to Alzheimer's disease. In the present study, we provide the first evidence of increased hypothalamic signalling via GSK3ß in leptin-deficient Lep(ob/ob) mice and show that intracerebroventricular injection of a GSK3ß inhibitor acutely improves glucose tolerance in these mice. The beneficial effect of the GSK3ß inhibitor was dependent on hypothalamic signalling via PI3K (phosphoinositide 3-kinase), a key intracellular mediator of both leptin and insulin action. Conversely, neuron-specific overexpression of GSK3ß in the mediobasal hypothalamus exacerbated the hyperphagia, obesity and impairment of glucose tolerance induced by a high-fat diet, while having little effect in controls fed standard chow. These results demonstrate that increased hypothalamic GSK3ß signalling contributes to deleterious effects of leptin deficiency and exacerbates high-fat diet-induced weight gain and glucose intolerance.

Rest phase snacking increases energy resorption and weight gain in male mice.

OBJECTIVE: Snacking, i.e., the intake of small amounts of palatable food items, is a common behavior in modern societies, promoting overeating and obesity. Shifting food intake into the daily rest phase disrupts circadian rhythms and is also known to stimulate weight gain. We therefore hypothesized that chronic snacking in the inactive phase may promote body weight gain and that this effect is based on disruption of circadian clocks. METHODS: Male mice were fed a daily chocolate snack either during their rest or their active phase and body weight development and metabolic parameters were investigated. Snacking experiments were repeated in constant darkness and in clock-deficient mutant mice to examine the role of external and internal time cues in mediating the metabolic effects of snacking. RESULTS: Chronic snacking in the rest phase increased body weight gain and disrupted metabolic circadian rhythms in energy expenditure, body temperature, and locomotor activity. Additionally, these rest phase snacking mice assimilated more energy during the inactive phase. Body weight remained increased in rest phase snacking wildtype mice in constant darkness as well as in clock-deficient mutant mice under a regular light-dark cycle compared to mice snacking in the active phase. Weight gain effects were abolished in clock-deficient mice in constant darkness. CONCLUSIONS: Our data suggest that mistimed snacking increases energy resorption and promotes body weight gain. This effect requires a functional circadian clock at least under constant darkness conditions.

Tomography of Feshbach resonance states.

Feshbach resonances are fundamental to interparticle interactions and become particularly important in cold collisions with atoms, ions, and molecules. In this work, we present the detection of Feshbach resonances in a benchmark system for strongly interacting and highly anisotropic collisions: molecular hydrogen ions colliding with noble gas atoms. The collisions are launched by cold Penning ionization, which exclusively populates Feshbach resonances that span both short- and long-range parts of the interaction potential. We resolved all final molecular channels in a tomographic manner using ion-electron coincidence detection. We demonstrate the nonstatistical nature of the final-state distribution. By performing quantum scattering calculations on ab initio potential energy surfaces, we show that the isolation of the Feshbach resonance pathways reveals their distinctive fingerprints in the collision outcome.

Monotonically convergent optimization in quantum control using Krotov's method.

The non-linear optimization method developed by A. Konnov and V. Krotov [Autom. Remote Cont. (Engl. Transl.) 60, 1427 (1999)] has been used previously to extend the capabilities of optimal control theory from the linear to the non-linear Schrödinger equation [S. E. Sklarz and D. J. Tannor, Phys. Rev. A 66, 053619 (2002)]. Here we show that based on the Konnov-Krotov method, monotonically convergent algorithms are obtained for a large class of quantum control problems. It includes, in addition to nonlinear equations of motion, control problems that are characterized by non-unitary time evolution, nonlinear dependencies of the Hamiltonian on the control, time-dependent targets, and optimization functionals that depend to higher than second order on the time-evolving states. We furthermore show that the nonlinear (second order) contribution can be estimated either analytically or numerically, yielding readily applicable optimization algorithms. We demonstrate monotonic convergence for an optimization functional that is an eighth-degree polynomial in the states. For the "standard" quantum control problem of a convex final-time functional, linear equations of motion and linear dependency of the Hamiltonian on the field, the second-order contribution is not required for monotonic convergence but can be used to speed up convergence. We demonstrate this by comparing the performance of first- and second-order algorithms for two examples.

Rovibrational dynamics of the strontium molecule in the A(1)Σ(u)+, c(3)Π(u), and a(3)Σ(u)+ manifold from state-of-the-art ab initio calculations.

State-of-the-art ab initio techniques have been applied to compute the potential energy curves for the electronic states in the A(1)Σ(u)(+), c(3)Π(u), and a(3)Σ(u)(+) manifold of the strontium dimer, the spin-orbit and nonadiabatic coupling matrix elements between the states in the manifold, and the electric transition dipole moment from the ground X(1)Σ(g)(+) to the nonrelativistic and relativistic states in the A+c+a manifold. The potential energy curves and transition moments were obtained with the linear response (equation of motion) coupled cluster method limited to single, double, and linear triple excitations for the potentials and limited to single and double excitations for the transition moments. The spin-orbit and nonadiabatic coupling matrix elements were computed with the multireference configuration interaction method limited to single and double excitations. Our results for the nonrelativistic and relativistic (spin-orbit coupled) potentials deviate substantially from recent ab initio calculations. The potential energy curve for the spectroscopically active (1)0(u)(+) state is in quantitative agreement with the empirical potential fitted to high-resolution Fourier transform spectra [A. Stein, H. Knöckel, and E. Tiemann, Eur. Phys. J. D 64, 227 (2011)]. The computed ab initio points were fitted to physically sound analytical expressions, and used in converged coupled channel calculations of the rovibrational energy levels in the A+c+a manifold and line strengths for the A(1)Σ(u)(+)←X(1)Σ(g (+) transitions. Positions and lifetimes of quasi-bound Feshbach resonances lying above the (1)S(0) + (3)P(1) dissociation limit were also obtained. Our results reproduce (semi)quantitatively the experimental data observed thus far. Predictions for on-going and future experiments are also reported.