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This work investigates and describes the structural dynamics taking place following charge-transfer-to-solvent photo-abstraction of electrons from I - and Br - ions in aqueous solution following single- and 2-photon excitation at 202 nm and 400 nm, respectively. A Time-Resolved X-ray Solution Scattering (TR-XSS) approach with direct sensitivity to the structure of the surrounding solvent as the water molecules adopt a new equilibrium configuration following the electron-abstraction process is utilized to investigate the structural dynamics of solvent shell expansion and restructuring in real-time. The structural sensitivity of the scattering data enables a quantitative evaluation of competing models for the interaction between the nascent neutral species and surrounding water molecules. Taking the I 0 -O distance as the reaction coordinate, we find that the structural reorganization is delayed by 0.1 ps with respect to the photoexcitation and completes on a time scale of 0.5-1 ps. On longer time scales we determine from the evolution of the TR-XSS difference signal that I 0 : e - recombination takes place on two distinct time scales of ∼20 ps and 100 s of picoseconds. These dynamics are well captured by a simple model of diffusive evolution of the initial photo-abstracted electron population where the charge-transfer-to-solvent process gives rise to a broad distribution of electron ejection distances, a significant fraction of which are in the close vicinity of the nascent halogen atoms and recombine on short time scales., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Alpha-gal IgE level can change rapidly. Reassessment of a patient's alpha-gal IgE level may be helpful in the patient's clinical follow-up. Pruritus related to the site of a previous tick bite strengthens the diagnosis of alpha-gal syndrome., Competing Interests: Supported by the Independent Research Fund Denmark (grant 2034-00031B [to K.B.L-M.]), the 10.13039/501100010234Swedish Asthma and Allergy Association Research Foundation (to M.vH.), the Swedish Cancer and 10.13039/501100013499Allergy Foundation (to M.vH.), the King Gustaf V 80th Birthday Foundation (to M.vH.), the 10.13039/501100003793Swedish Heart-Lung Foundation (to M.vH.), and the Hesselman Foundation (to M.vH.). Disclosure of potential conflict of interest: K. B. Leth-Møller has received lecture fees from 10.13039/100011033Thermo Fisher Scientific. M. van Hage has received lecture fees from 10.13039/100011033Thermo Fisher Scientific and 10.13039/100004325AstraZeneca outside the submitted work. The rest of the authors declare that they have no relevant conflicts of interest. Informed patient consent for publication: Signed informed consent was obtained from the patient., (© 2024 The Authors.)

Background: Allergic rhinitis (AR) is one of the most common chronic diseases worldwide. There are limited prospective long-term data regarding persistency and remission of AR. The objective of this study was to investigate the natural course of pollen-induced AR (pollen-AR) over 20 years, from childhood into early adulthood., Methods: Data from 1137 subjects in the Barn/Children Allergi/Allergy Milieu Stockholm Epidemiologic birth cohort (BAMSE) with a completed questionnaire regarding symptoms, asthma, treatment with allergen immunotherapy (AIT) and results of allergen-specific IgE for inhalant allergens at 4, 8, 16 and 24 years were analyzed. Pollen-AR was defined as sneezing, runny, itchy or blocked nose; and itchy or watery eyes when exposed to birch and/or grass pollen in combination with allergen-specific IgE ≥0.35kU A /L to birch and/or grass., Results: Approximately 75% of children with pollen-AR at 4 or 8 years had persistent disease up to 24 years, and 30% developed asthma. The probability of persistency was high already at low levels of pollen-specific IgE. The highest rate of remission from pollen-AR was seen between 16 and 24 years (21.5%); however, the majority remained sensitized. This period was also when pollen-specific IgE-levels stopped increasing and the average estimated annual incidence of pollen-AR decreased from 1.5% to 0.8% per year., Conclusion: Children with pollen-AR are at high risk of persistent disease for at least 20 years. Childhood up to adolescence seems to be the most dynamic period of AR progression. Our findings underline the close cross-sectional and longitudinal relationship between sensitization, AR and asthma., (© 2023 The Authors. Allergy published by European Academy of Allergy and Clinical Immunology and John Wiley & Sons Ltd.)

Aim: To examine trends in all body mass index (BMI) groups in children from 1936 to 2011., Methods: We included 197 694 girls and 201 276 boys from the Copenhagen School Health Records Register, born between 1930 and 1996, with longitudinal weight and height measurements (6-14 years). Using International Obesity Task Force criteria, BMI was classified as underweight, normal-weight, overweight and obesity. Sex- and age-specific prevalences were calculated., Results: From the 1930s, the prevalence of underweight was stable until a small increase occurred from 1950 to 1970s, and thereafter it declined into the early 2000s. Using 7-year-olds as an example, underweight changed from 10% to 7% in girls and from 9% to 6% in boys during the study period. The prevalence of overweight plateaued from 1950 to 1970s and then steeply increased from 1970s onwards and in 1990-2000s 15% girls and 11% boys at 7 years had overweight. The prevalence of obesity particularly increased from 1980s onwards and in 1990-2000s 5% girls and 4% boys at 7 years had obesity. These trends slightly differed by age., Conclusion: Among Danish schoolchildren, the prevalence of underweight was greater than overweight until the 1980s and greater than obesity throughout the period. Thus, monitoring the prevalence of childhood underweight remains an important public health issue., (© 2023 The Authors. Acta Paediatrica published by John Wiley & Sons Ltd on behalf of Foundation Acta Paediatrica.)

Structural studies using x-ray scattering methods for investigating molecules in solution are shifting focus toward describing the role and effects of the surrounding solvent. However, forward models based on molecular dynamics (MD) simulations to simulate structure factors and x-ray scattering from interatomic distributions such as radial distribution functions (RDFs) face limitations imposed by simulations, particularly at low values of the scattering vector q. In this work, we show how the value of the structure factor at q = 0 calculated from RDFs sampled from finite MD simulations is effectively dependent on the size of the simulation cell. To eliminate this error, we derive a new scheme to renormalize the sampled RDFs based on a model of the excluded volume of the particle-pairs they were sampled from, to emulate sampling from an infinite system. We compare this new correction method to two previous RDF-correction methods, developed for Kirkwood-Buff theory applications. We present a quantitative test to assess the reliability of the simulated low-q scattering signal and show that our RDF-correction successfully recovers the correct q = 0 limit for neat water. We investigate the effect of MD-sampling time on the RDF-corrections, before advancing to a molecular example system, comprised of a transition metal complex solvated in a series of water cells with varying densities. We show that our correction recovers the correct q = 0 behavior for all densities. Furthermore, we employ a simple continuum scattering model to dissect the total scattering signal from the solvent-solvent structural correlations in a solute-solvent model system to find two distinct contributions: a non-local density-contribution from the finite, fixed cell size in NVT simulations, and a local contribution from the solvent shell. We show how the second contribution can be approximated without also including the finite-size contribution. Finally, we provide a "best-practices"-checklist for experimentalists planning to incorporate explicit solvation MD simulations in future work, offering guidance for improving the accuracy and reliability of structural studies using x-ray scattering methods in solution., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

We apply ultrashort X-ray laser pulses to track optically excited structural dynamics of [Ir 2 (dimen) 4 ] 2+ molecules in solution. In our exploratory study we determine angular correlations in the scattered X-rays, which comprise a complex fingerprint of the ultrafast dynamics. Model-assisted analysis of the experimental correlation data allows us to elucidate various aspects of the photoinduced changes in the excited molecular ensembles. We unambiguously identify that in our experiment the photoinduced transition dipole moments in [Ir 2 (dimen) 4 ] 2+ molecules are oriented perpendicular to the Ir-Ir bond. The analysis also shows that the ground state conformer of [Ir 2 (dimen) 4 ] 2+ with a larger Ir-Ir distance is mostly responsible for the formation of the excited state. We also reveal that the ensemble of solute molecules can be characterized with a substantial structural heterogeneity due to solvent influence. The proposed X-ray correlation approach offers an alternative path for studies of ultrafast structural dynamics of molecular ensembles in the liquid and gas phases.

We present a fully self-consistent polarizable embedding (PE) model that does not suffer from unphysical boundary polarization. This is achieved through the use of the minimum-image convention (MIC) in the induced electrostatics. It is a simple yet effective approach that includes a more physically accurate description of the polarization throughout the molecular system. Using PE with MIC (PE-MIC), we shed new light on the limitations of commonly employed cutoff models, such as the droplet model, when used in PE calculations. Specifically, we investigate the effects of the unphysical polarization at the outer boundary by comparing induced dipoles and the associated electrostatic potentials, as well as some optical properties of solute-solvent and biomolecular systems. We show that the magnitude of the inaccuracies caused by the unphysical polarization depends on multiple parameters: the nature of the quantum subsystem and of the environment, the cutoff model and distance, and the calculated property.

Objective: Evidence linking childhood body mass index (BMI) with subsequent eating disorders is equivocal. Potential explanations include different study populations and size, and that anorexia nervosa (AN) and bulimia nervosa (BN) should be studied separately. We examined whether birthweight and childhood BMI were associated with subsequent risk of AN and BN in girls., Method: We included 68,793 girls from the Copenhagen School Health Records Register born between 1960 and 1996 with information on birthweight and measured weights and heights obtained from school health examinations at ages 6-15 years. Diagnoses of AN and BN were retrieved from Danish nationwide patient registers. We used Cox proportional hazards regression to estimate hazard ratios (HRs) and 95% confidence intervals (CIs)., Results: We identified 355 cases of AN (median age: 19.0) and 273 cases of BN (median age: 21.8). Higher childhood BMI was linearly associated with decreasing risk of AN and increasing risk of BN at all childhood ages. At age 6, the HR for AN was 0.85 (95% CI: 0.74-0.97) per BMI z-score and the HR for BN was 1.78 (95% CI: 1.50-2.11) per BMI z-score. Birthweight >3.75 kg was associated with increased risk of BN compared to a birthweight of 3.26-3.75 kg., Conclusion: Higher BMI in girls at ages 6-15 years was associated with decreasing risk of AN and increasing risk of BN. Premorbid BMI could be relevant for the etiology of AN and BN, and in identifying high risk individuals., Public Significance: Eating disorders are associated with elevated mortality, especially AN. Using a cohort of Copenhagen school children, we linked information on BMI at ages 6-15 years for 68,793 girls with nationwide patient registers. Low childhood BMI was associated with increased risk of AN, whereas high childhood BMI was associated with increased risk of BN. These findings may assist clinicians in identifying individuals at high-risk of these diseases., (© 2023 The Authors. International Journal of Eating Disorders published by Wiley Periodicals LLC.)

Single-ion magnets (SIMs) constitute the ultimate size limit in the quest for miniaturizing magnetic materials. Several bottlenecks currently hindering breakthroughs in quantum information and communication technologies could be alleviated by new generations of SIMs displaying multifunctionality. Here, ultrafast optical absorption spectroscopy and X-ray emission spectroscopy are employed to track the photoinduced spin-state switching of the prototypical complex [Co(terpy) 2 ] 2+ (terpy = 2,2':6',2″-terpyridine) in solution phase. The combined measurements and their analysis supported by density functional theory (DFT), time-dependent-DFT (TD-DFT) and multireference quantum chemistry calculations reveal that the complex undergoes a spin-state transition from a tetragonally elongated doublet state to a tetragonally compressed quartet state on the femtosecond timescale, i.e., it sustains ultrafast Jahn-Teller (JT) photoswitching between two different spin multiplicities. Adding new Co-based complexes as possible contenders in the search for JT photoswitching SIMs will greatly widen the possibilities for implementing magnetic multifunctionality and eventually controlling ultrafast magnetization with optical photons., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The time-resolved x-ray absorption spectrum of the BT-1T cation (BT-1T + ) is theoretically simulated in order to investigate the charge transfer reaction of the system. We employ both trajectory surface hopping and quantum dynamics to simulate the structural evolution over time and the changes in the state populations. To compute the static x-ray absorption spectra (XAS) of the ground and excited states, we apply both the time-dependent density functional theory and the coupled cluster singles and doubles method. The results obtained are in good agreement between the methods. It is, furthermore, found that the small structural changes that occur during the reaction have little effect on the static XAS. Hence, the tr-XAS can be computed based on the state populations determined from a nuclear dynamics simulation and one set of static XAS calculations, utilizing the ground state optimized geometry. This approach can save considerable computational resources, as the static spectra need not to be calculated for all geometries. As BT-1T is a relatively rigid molecule, the outlined approach should only be considered when investigating non-radiative decay processes in the vicinity of the Franck-Condon point., Competing Interests: The authors have no conflicts to disclose., (© 2023 Author(s).)

Background and Aim: It is generally accepted that functional somatic disorders (FSDs) are a product of biological, psychological, and social factors. Social position might be part of this complex, but the literature on this issue is currently heterogeneous and inconsistent. The aim of the present study was - in a population-based cohort - to test the hypothesis that lower social position would be associated with higher a risk of FSD., Method: The association between social position and FSD was examined in a cross-sectional study with various measures of social position (education as measured by vocational training; employment; cohabitation; subjective social status) and delimitations of FSD (irritable bowel syndrome, chronic fatigue syndrome, fibromyalgia, bodily distress syndrome, and symptom profiles). The associations were analyzed using logistic regressions to calculate odds ratios and 95% confidence intervals. Each social measure was analyzed independently and was adjusted for age and sex., Results: Lower levels of vocational training, being unemployed, and living alone were associated with higher risk of FSD, regardless of the FSD delimitation. There was also a significant negative association between subjective evaluated social status and FSD. The associations remained after multiple adjustments, and seemed to be strongest for the more severe FSD-types., Conclusions: Lower social position is associated with higher risk of FSD, especially the more severe FSD delimitations, which might constitute an especially vulnerable group. However, the mechanisms behind the relations remain unknown.

We present a sub-picosecond resolved investigation of the structural solvent reorganization and geminate recombination dynamics following 400 nm two-photon excitation and photodetachment of a valence p electron from the aqueous atomic solute, I - (aq). The measurements utilized time-resolved X-ray Absorption Near Edge Structure (TR-XANES) spectroscopy and X-ray Solution Scattering (TR-XSS) at the Linac Coherent Light Source x-ray free electron laser in a laser pump/x-ray probe experiment. The XANES measurements around the L 1 -edge of the generated nascent iodine atoms (I 0 ) yield an average electron ejection distance from the iodine parent of 7.4 ± 1.5 Å with an excitation yield of about 1/3 of the 0.1M NaI aqueous solution. The kinetic traces of the XANES measurement are in agreement with a purely diffusion-driven geminate iodine-electron recombination model without the need for a long-lived (I 0 :e - ) contact pair. Nonequilibrium classical molecular dynamics simulations indicate a delayed response of the caging H 2 O solvent shell and this is supported by the structural analysis of the XSS data: We identify a two-step process exhibiting a 0.1 ps delayed solvent shell reorganization time within the tight H-bond network and a 0.3 ps time constant for the mean iodine-oxygen distance changes. The results indicate that most of the reorganization can be explained classically by a transition from a hydrophilic cavity with a well-ordered first solvation shell (hydrogens pointing toward I - ) to an expanded cavity around I 0 with a more random orientation of the H 2 O molecules in a broadened first solvation shell.

We investigate the resonant and non-resonant Auger spectra of ozone with a newly implemented multi-reference protocol based on the one-center approximation [Tenorio et al. , J. Chem. Theory Comput. 2022, 18 , 4387-4407]. The results of our calculations are compared to existing experimental data, where we elucidate the resonant Auger spectrum measured at 530.8 and 536.7 eV, that correspond to the 1s O T → π*(2b 1 ) and 1s O T → σ*(7a 1 ) resonances, and at 542.3 eV, which lies near the 1s O C → σ *(7a 1 ) excited state and above the 1s O T -1 ionization threshold. Using molecular dynamics simulations, we demonstrate the relevance of few-femtoseconds nuclear dynamics in the resonant Auger spectrum of ozone following the 1s O T → π*(2b 1 ) core-excitation.

The ultrafast dynamical response of solute-solvent interactions plays a key role in transition metal complexes, where charge transfer states are ubiquitous. Nonetheless, there exist very few excited-state simulations of transition metal complexes in solution. Here, we carry out a nonadiabatic dynamics study of the iron complex [Fe(CN) 4 (bpy)] 2- (bpy = 2,2'-bipyridine) in explicit aqueous solution. Implicit solvation models were found inadequate for reproducing the strong solvatochromism in the absorption spectra. Instead, direct solute-solvent interactions, in the form of hydrogen bonds, are responsible for the large observed solvatochromic shift and the general dynamical behavior of the complex in water. The simulations reveal an overall intersystem crossing time scale of 0.21 ± 0.01 ps and a strong reliance of this process on nuclear motion. A charge transfer character analysis shows a branched decay mechanism from the initially excited singlet metal-to-ligand charge transfer ( 1 MLCT) states to triplet states of 3 MLCT and metal-centered ( 3 MC) character. We also find that solvent reorganization after excitation is ultrafast, on the order of 50 fs around the cyanides and slower around the bpy ligand. In contrast, the nuclear vibrational dynamics, in the form of Fe-ligand bond changes, takes place on slightly longer time scales. We demonstrate that the surprisingly fast solvent reorganizing should be observable in time-resolved X-ray solution scattering experiments, as simulated signals show strong contributions from the solute-solvent scattering cross term. Altogether, the simulations paint a comprehensive picture of the coupled and concurrent electronic, nuclear, and solvent dynamics and interactions in the first hundreds of femtoseconds after excitation.

Background: Previous observational studies have indicated a protective effect of drinking milk on asthma and allergy. In Mendelian Randomization, one or more genetic variants are used as unbiased markers of exposure to examine causal effects. We examined the causal effect of milk intake on hay fever, asthma, forced expiratory volume in one second (FEV1) and forced vital capacity (FVC) by using the lactase rs4988235 genotype associated with milk intake., Methods: We performed a Mendelian Randomization study including 363,961 participants from the UK Biobank., Results: Observational analyses showed that self-reported milk-drinkers vs. non-milk drinkers had an increased risk of hay fever: odds ratio (OR) = 1.36 (95% CI 1.32, 1.40, p < 0.001), asthma: OR = 1.33 (95% CI 1.38, 1.29, p < 0.001), yet a higher FEV1: β = 0.022 (SE = 0.004, p < 0.001) and FVC: β = 0.026 (SE = 0.005, p < 0.001). In contrast, genetically determined milk-drinking vs. not drinking milk was associated with a lower risk of hay fever: OR = 0.791 (95% CI 0.636, 0.982, p = 0.033), and asthma: OR = 0.587 (95% CI 0.442, 0.779, p = 0.001), and lower FEV1: β = - 0.154 (standard error, SE = 0.034, p < 0.001) liter, and FVC: β = - 0.223 (SE = 0.034, p < 0.001) liter in univariable MR analyses. These results were supported by multivariable Mendelian randomization analyses although not statistically significant., Conclusions: As opposed to observational results, genetic association findings indicate that drinking milk has a protective effect on hay fever and asthma but may also have a negative effect on lung function. The results should be confirmed in other studies before any recommendations can be made., (© 2021. Springer Nature B.V.)

A full-dimensional wavepacket propagation describing the bimolecular exchange reactions H + H'OD → H'OH + D or HOD + H' initiated by photolysis of HCl in the hydrogen-bound complex (HCl)⋯(HOD) is reported. The dynamics of this reaction is carried out with the MCTDH method on an ab initio potential energy surface (PES) of H 3 O and the initial state is derived from the ground state wavefunction of the complex obtained by relaxation on its own electronic ground state ab initio PES. The description of the system makes use of polyspherical coordinates parametrizing a set of Radau and Jacobi vectors. The calculated energy- and time-resolved reaction probabilities show, owing to the large collision energies at play stemming from the (almost full) photolysis of HCl, that the repulsion between oxygen in the H'OD molecule and the incoming hydrogen atom is the main feature of the collision and leads to non-reactive scattering. No abstraction reaction products are observed. However, both exchange processes are still observable, with a preference in O-H' bond dissociation over that of O-D. The selectivity is reversed upon vibrational pre-excitation of the O-D stretching mode in the H'OD molecule. It is shown that, after the collision, the hydrogen atom of HCl does most likely not encounter the almost stationary chlorine atom again but we also consider the limit case where the H atom is forced to collide multiple times against H'OD as a result of being pushed back by the Cl atom.

The excess energy flow pathways during rotational and translational relaxation induced by rotational or translational excitation of a single molecule of and within each of four different neat liquids (H 2 O, MeOH, CCl 4 , and CH 4 ) are studied using classical molecular dynamics simulations and energy flux analysis. For all four liquids, the relaxation processes for both types of excitation are ultrafast, but the energy flow is significantly faster for the polar, hydrogen-bonded (H-bonded) liquids H 2 O and MeOH. Whereas the majority of the initial excess energy is transferred into hindered rotations (librations) for rotational excitation in the H-bonded liquids, an almost equal efficiency for transfer to translational and rotational motions is observed in the nonpolar, non-H-bonded liquids CCl 4 and CH 4 . For translational excitation, transfer to translational motions dominates for all liquids. In general, the energy flows are quite local; i.e., more than 70% of the energy flows directly to the first solvent shell molecules, reaching almost 100% for CCl 4 and CH 4 . Finally, the determined validity of linear response theory for these nonequilibrium relaxation processes is quite solvent-dependent, with the deviation from linear response most marked for rotational excitation and for the nonpolar liquids.

Electronic relaxation in organic chromophores often proceeds via states not directly accessible by photoexcitation. We report on the photoinduced dynamics of pyrazine that involves such states, excited by a 267 nm laser and probed with X-ray transient absorption spectroscopy in a table-top setup. In addition to the previously characterized 1 B 2u (ππ*) (S 2 ) and 1 B 3u (nπ*) (S 1 ) states, the participation of the optically dark 1 A u (nπ*) state is assigned by a combination of experimental X-ray core-to-valence spectroscopy, electronic structure calculations, nonadiabatic dynamics simulations, and X-ray spectral computations. Despite 1 A u (nπ*) and 1 B 3u (nπ*) states having similar energies at relaxed geometry, their X-ray absorption spectra differ largely in transition energy and oscillator strength. The 1 A u (nπ*) state is populated in 200 ± 50 femtoseconds after electronic excitation and plays a key role in the relaxation of pyrazine to the ground state., (© 2021. The Author(s).)

We present a computational study on nonadiabatic excited-state dynamics initiated from the 3p Rydberg states of trimethylamine (TMA). We utilise a methodology based on full-dimensional (39 D) trajectory surface-hopping (TSH) simulations, in which propagation is carried out on on-the-fly density functional theory (DFT)/time-dependent DFT (TD-DFT) potentials. Both our electronic structure benchmarks to high-level ab initio methods (EOM-CCSD, CASPT2) and TSH simulations demonstrate high-accuracy of the applied CAM-B3LYP functional for the description of Rydberg excited states. Based on our excited-state simulations, we construct the following mechanistic picture: when pumped resonantly to the 3p Rydberg manifold, TMA coherently vibrates along the planarisation mode with a period of 104 fs and an exponential coherence decay time constant of 240 fs. Nonadiabatic dynamics occur on a faster (∼1 ps) and a slower (∼3 ps) timescale, along the N-C stretching mode by mixing with a dissociative σN-C* state. As a minor relaxation channel, 3p → 3s internal conversion occurs via branching at the σN-C*/3s intersection. We find that photodissociaton is hardly observable within 3 ps (1%), which is a failure of the range-separated hybrid CAM-B3LYP functional, as a consequence of its static electron correlation deficiency at long range. In contrast, pure DFT (GGA-BLYP) provides an accurate long-range description (19% dissociation yield), also supported by comparison to recent ultrafast experiments, even if the Rydberg state energies are significantly underestimated (>1 eV). Finally, we reveal the crucial role of vibrational coherence and energy transfer from the planarisation mode for N-C bond activation and resulting nonadiabatic dynamics. The present work illustrates the importance of nuclear-electronic coupling for excited-state dynamics and branching at conical intersections.

We assess the performance of different protocols for simulating excited-state x-ray absorption spectra. We consider three different protocols based on equation-of-motion coupled-cluster singles and doubles, two of them combined with the maximum overlap method. The three protocols differ in the choice of a reference configuration used to compute target states. Maximum-overlap-method time-dependent density functional theory is also considered. The performance of the different approaches is illustrated using uracil, thymine, and acetylacetone as benchmark systems. The results provide guidance for selecting an electronic structure method for modeling time-resolved x-ray absorption spectroscopy., (© 2021 Author(s).)

Background: Studies have indicated that underdiagnosis and diagnostic delay are common in celiac disease. Therefore, it is important to increase our knowledge of what symptoms and biomarkers could identify undiagnosed cases of celiac disease., Methods: We screened for celiac disease antibodies in stored blood samples from 16,776 participants in eight population-based studies examined during 1976-2012. Undiagnosed celiac seropositivity was defined as celiac disease antibody positivity (IgG-deamidated gliadin peptide above 10.0 U/mL and/or IgA-tissue transglutaminase (TTG) or IgG-TTG above 7.0 U/mL) without a known diagnosis of celiac disease in the National Patient Register. In all studies general health symptoms were recorded by participant-completed questionnaire, including self-perceived health, tiredness, headache and gastrointestinal symptoms. Furthermore, blood samples were drawn for analyses of biomarkers e.g. hemoglobin, blood glucose, cholesterol, liver parameters and vitamins. The participants with undiagnosed celiac seropositivity were matched by sex, age and study with four controls among the celiac disease antibody negative participants., Results: We excluded, five participants with known celiac disease, resulting in a population of 16,771 participants. In this population 1% (169/16,771) had undiagnosed celiac seropositivity. There were no statistically significant differences in symptoms between cases and controls. Undiagnosed celiac seropositivity was associated with low blood cholesterol (< 5 mmol/L) and low hemoglobin (< 7.3 mmol/L for women and < 8.3 mmol/L for men)., Conclusion: In this general population study, undiagnosed cases of celiac seropositivity did not have more symptoms than controls, confirming the diagnostic difficulties of celiac disease and the low prognostic value of symptoms for a diagnosis of celiac disease. Furthermore, decreased levels of cholesterol and/or hemoglobin in the blood were associated with undiagnosed celiac seropositivity.

Background: Important insights on, for example, prevalence, disease progression, and treatment of allergic rhinitis can be obtained from large-scale database studies if researchers are able to identify allergic individuals. We aimed to assess the validity of 13 different algorithms based on Danish nationwide prescription and/or hospital data to identify adults with allergic rhinitis., Methods: Our primary gold standard of allergic rhinitis was a positive serum specific IgE (≥0.35) and self-reported nasal symptoms retrieved from two general health examination studies conducted in Danish adults (18-69 years) during 2006 to 2008 (n = 3416) and 2012 to 2015 (n = 7237). The secondary gold standard of allergic rhinitis was self-reported physician diagnosis. We calculated sensitivity, specificity, positive predictive value (PPV), negative predictive value, and corresponding 95% confidence intervals (95% CI) for each register-based algorithm in the two time periods., Results: Sensitivity (≤0.40) was low for all algorithms irrespective of definition of allergic rhinitis (gold standard) or time period. The highest PPVs were obtained for algorithms requiring both antihistamines and intranasal corticosteroids; yielding a PPV of 0.69 (0.62-0.75) and a corresponding sensitivity of 0.10 (0.09-0.12) for the primary gold standard of allergic rhinitis in 2012 to 2015., Conclusion: Algorithms based on both antihistamines and intranasal corticosteroids yielded the highest PPVs. However, the PPVs were still moderate and came at the expense of low sensitivity when applying the strict primary gold standard (sIgE and nasal symptom)., (© 2020 John Wiley & Sons Ltd.)

Background: Only a limited number of studies have included objective measures of allergic sensitisation (such as skin-prick test [SPT] and serum specific IgE [sIgE]) when studying time trends in allergic respiratory disease in adults within the current millennium., Methods: Five health examination studies of random samples of individuals aged 18-69 years resident in the Copenhagen region were conducted in 1990-1991, 2006-2008, 2010-2011, 2012-2015, and 2016-2017. Allergic sensitisation was defined by sIgE (in 1990-1991, 2006-2008, and, 2012-2015) or SPT (in 2006-2008, 2010-2011, and 2016-2017) to at least one of the allergens: birch, grass, house dust mite, or cat. Allergic rhinitis was defined as sensitisation and self-reported nasal symptoms., Results: The age- and sex-standardised prevalence of sIgE-defined sensitisation increased from 16% in 1990-1991, to 26% in 2006-2008, and to 29% in 2012-2015. The age- and sex-standardised prevalence of SPT-defined sensitisation increased from 27% in 2006-2008, to 28% in 2010-2011, and to 32% in 2016-2017. Changes in sIgE-defined and SPT-defined allergic rhinitis showed similar increasing trends., Conclusion: The prevalence of allergic sensitisation and allergic rhinitis increased in a general adult Danish population over the last three decades and has thus continued to increase in the current millennium., (© 2020 EAACI and John Wiley and Sons A/S. Published by John Wiley and Sons Ltd.)

The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip) 2 ] 2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered ( 3 MC) excited state surface. This 3 MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a 3 MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.

Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an Fe II NHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3 MLCT state, from the initially excited 1 MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3 MC state, in competition with vibrational relaxation and cooling to the relaxed 3 MLCT state. The relaxed 3 MLCT state then decays much more slowly (7.6 ps) to the 3 MC state. The 3 MC state is rapidly (2.2 ps) deactivated to the ground state. The 5 MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3 MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

As a demonstration of the analysis of the electronic structure and the nuclear dynamics from time-resolved near-edge X-ray absorption fine structure (TR-NEXAFS), we present the TR-NEXAFS spectra of pyrazine following the excitation to the 1 B 2u (ππ * ) state. The spectra are calculated combining the frozen-core/core-valence separated equation-of-motion coupled cluster singles and doubles approach for the spectral signatures and the multiconfiguration time-dependent Hartree method for the wave packet propagation. The population decay from the 1 B 2u (ππ * ) state to the 1 B 3u (nπ * ) and 1 A u (nπ * ) states, followed by oscillatory flow of population between the 1 B 3u (nπ * ) and 1 A u (nπ * ) states, is interpreted by means of visualization of the potential energy curves and the reduced nuclear densities. By examining the electronic structure of the three valence-excited states and the final core-excited states, we observe that the population dynamics is explicitly reflected in the TR-NEXAFS spectra, especially when the heteroatoms are selected as the X-ray absorption sites. This work illustrates the feasibility of extracting fine details of molecular photophysical processes from TR-NEXAFS spectra by using currently available theoretical methods.

Simulation of the ultrafast excited-state dynamics and elastic X-ray scattering of the [Fe(bmip) 2 ] 2+ [bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-4-pyridine] complex is presented and analyzed. We employ quantum wavepacket dynamics simulations on a 5-dimensional potential energy surface (PES) calculated by time-dependent density functional theory with 26 coupled diabatic states. The simulations are initiated by explicit inclusion of a time-dependent electromagnetic field. In the case of resonant excitation into singlet metal-to-ligand charge transfer ( 1 MLCT) states, kinetic (exponential) population dynamics are observed with small nuclear motion. In agreement with transient optical absorption spectroscopy experiments, we observe a subpicosecond 1 MLCT → 3 MLCT intersystem crossing and a subsequent decay into triplet metal-centered ( 3 MC) states on a picosecond time scale. The simulated time-resolved difference scattering signal is dominated by the 3 MC component, for which the structural distortions are significant. On the other hand, excitation into 1 MC states leads to ballistic (nonexponential) population dynamics with strong nuclear motion. The reason for these ballistic dynamics is that in this case, the excitation occurs into a nonequilibrium region, i.e., far from the minimum of the 1 MC PES. This results in wavepacket dynamics along the principal breathing mode, which is clearly visible in both the population dynamics and difference scattering. Finally, the importance of decomposing the difference scattering into components by electronic states is highlighted, information which is not accessible from elastic X-ray scattering experiments.

The photoinduced ring-opening reaction is a key process in the functioning of dihydroazulene/vinylheptafulvene (DHA/VHF) photoswitches. Over the years, the mechanism of this reaction has been extensively debated. Herein, by means of nonadiabatic trajectory dynamics simulations and quantum chemistry calculations, we present the first detailed and comprehensive investigation on the mechanism of the photoinduced ring-opening reaction of DHA. The results show the crucial role of the excited-state ring planarization process for the bond breaking. Our dynamics simulations show that the DHA ring opening is an ultrafast reaction that does not follow exponential kinetics but exhibits ballistic dynamics. Upon photoexcitation, the planarization occurs within 300-500 fs. This leads to the ring-opening reaction and concurrent decay of the molecule to the ground state within 100 fs through an S 1 → S 0 internal conversion process toward forming the VHF isomer. These results are consistent with previous ultrafast time-resolved experiments and lead to a thorough understanding of the DHA/VHF photoconversion.

Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2'-bipyridine) 3 ] 2+ , where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.

We applied angular X-ray Cross-Correlation analysis (XCCA) to scattering images from a femtosecond resolution X-ray free-electron laser pump-probe experiment with solvated PtPOP {[Pt 2 (P 2 O 5 H 2 ) 4 ] 4- } metal complex molecules. The molecules were pumped with linear polarized laser pulses creating an excited state population with a preferred orientational (alignment) direction. Two time scales of 1.9 ± 1.5 ps and 46 ± 10 ps were revealed by angular XCCA associated with structural changes and rotational dephasing of the solvent molecules, respectively. These results illustrate the potential of XCCA to reveal hidden structural information in the analysis of time-resolved x-ray scattering data from molecules in solution.

Simulations of nonresonant ultrafast x-ray scattering from a molecular wave packet in H&#95;{2} are used to examine and classify the components that contribute to the total scattering signal. The elastic component, which can be used to determine the structural dynamics of the molecule, is also found to carry a strong signature of an adiabatic electron transfer that occurs in the simulated molecule. The inelastic component, frequently assumed to be constant, is found to change with the geometry of the molecule. Finally, a coherent mixed component due to interferences between different inelastic transitions is identified and shown to provide a direct probe of transient electronic coherences.

We report x-ray free electron laser experiments addressing ground-state structural dynamics of the diplatinum anion Pt&#95;{2}POP&#95;{4} following photoexcitation. The structural dynamics are tracked with <100  fs time resolution by x-ray scattering, utilizing the anisotropic component to suppress contributions from the bulk solvent. The x-ray data exhibit a strong oscillatory component with period 0.28 ps and decay time 2.2 ps, and structural analysis of the difference signal directly shows this as arising from ground-state dynamics along the PtPt coordinate. These results are compared with multiscale Born-Oppenheimer molecular dynamics simulations and demonstrate how off-resonance excitation can be used to prepare a vibrationally cold excited-state population complemented by a structure-dependent depletion of the ground-state population which subsequently evolves in time, allowing direct tracking of ground-state structural dynamics.

In this work, we investigate the excited-state solute and solvation structure of [Ru(bpy)3]2+, [Fe(bpy)3]2+, [Fe(bmip)2]2+ and [Cu(phen)2]+ (bpy = 2,2'-bipyridine; bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine; phen = 1,10-phenanthroline) transition metal complexes (TMCs) in terms of solute-solvent radial distribution functions (RDFs) and evaluate the performance of some of the most popular partial atomic charge (PAC) methods for obtaining these RDFs by molecular dynamics (MD) simulations. To this end, we compare classical MD of a frozen solute in water and acetonitrile (ACN) with quantum mechanics/molecular mechanics Born-Oppenheimer molecular dynamics (QM/MM BOMD) simulations. The calculated RDFs show that the choice of a suitable PAC method is dependent on the coordination number of the metal, denticity of the ligands, and type of solvent. It is found that this selection is less sensitive for water than ACN. Furthermore, a careful choice of the PAC method should be considered for TMCs that exhibit a free direct coordination site, such as [Cu(phen)2]+. The results of this work show that fast classical MD simulations with ChelpG/RESP or CM5 PACs can produce RDFs close to those obtained by QM/MM MD and thus, provide reliable solvation structures of TMCs to be used, e.g. in the analysis of scattering data.

Aims: To use the rs1229984 variant associated with alcohol consumption as an instrument for alcohol consumption to test the causality of the association of alcohol consumption with hay fever, asthma, allergic sensitization and serum total immunoglobulin (Ig)E., Design: Observational and Mendelian randomization analyses using genetic variants as unbiased markers of exposure to estimate causal effects, subject to certain assumptions., Setting: Europe., Participants: We included a total of 466 434 people aged 15-82 years from 17 population-based studies conducted from 1997 to 2015., Measurements: The rs1229984 (ADH1B) was genotyped; alcohol consumption, hay fever and asthma were self-reported. Specific and total IgE were measured from serum samples., Findings: Observational analyses showed that ever-drinking versus non-drinking, but not amount of alcohol intake, was positively associated with hay fever and inversely associated with asthma but not with allergic sensitization or serum total immunoglobulin (Ig)E. However, Mendelian randomization analyses did not suggest that the observational associations are causal. The causal odds ratio (OR) per genetically assessed unit of alcohol/week was an OR = 0.907 [95% confidence interval (CI) = 0.806, 1.019; P = 0.101] for hay fever, an OR = 0.897 (95% CI = 0.790, 1.019; P = 0.095) for asthma, an OR = 0.971 (95% CI =  0.804, 1.174; P = 0.763) for allergic sensitization and a 4.7% change (95% CI = -5.5%, 14.9%; P = 0.366) for total IgE., Conclusions: In observational analyses, ever-drinking versus not drinking was positively associated with hay fever and negatively associated with asthma. However, the Mendelian randomization results were not consistent with these associations being causal., (© 2018 Society for the Study of Addiction.)

Coherence is one of the most important phenomena in ultrafast sciences. We give our perspective on the terminology, observation, and preservation of coherence in photophysical processes with some glimpses to the past and some looking-head to what may pave the way for scaling one of the last bastions in ultrafast science, namely, that of mode specific chemistry where it will be possible to break any specific bond by tailoring the pulse, an accomplishment that obviously would be the dream of any chemist.

The excited-state dynamics of two functional Fe-carbene complexes, [Fe(bmip) 2 ] 2+ (bmip = 2,6-bis(3-methyl-imidazole-1-ylidene)-pyridine) and [Fe(btbip) 2 ] 2+ (btbip = 2,6-bis(3- tert-butyl-imidazole-1-ylidene)pyridine), are studied using the spin-vibronic model. In contrast to the usual projection of the ground state nuclear wave function onto an excited state surface, the dynamics are initiated by an explicit interaction term between the external time-dependent electric field (laser pulse) and the transition dipole moment of the molecule. The results show that the spin-vibronic model, as constructed directly from electronic structure calculations, exhibits erroneous, polarization-dependent relaxation dynamics stemming from artificial interference of coupled relaxation pathways. This is due to the lack of rotational invariance in the description of excitation into degenerate states. We introduce and discuss a correction using the spherical basis and complex transition dipole moments. This modification in the interaction Hamiltonian leads to rotationally invariant excitation and produces polarization-independent population dynamics.

Time-resolved X-ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X-ray free-electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV-Vis pump laser pulse with the sample, which induces anisotropic structural changes that can be captured by femtosecond X-ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural sensitivity of the time-resolved X-ray scattering experiment. This method is applied on time-resolved X-ray scattering patterns measured upon photoexcitation of a solvated di-platinum complex at an XFEL, and the key parameters involved are explored. It is shown that a combined analysis of the anisotropic and isotropic difference scattering signals in this experiment allows a more precise determination of the main photoinduced structural change in the solute, i.e. the change in Pt-Pt bond length, and yields more information on the excitation channels than the analysis of the isotropic scattering only. Finally, it is discussed how the anisotropic transient response of the solvent can enable the determination of key experimental parameters such as the instrument response function.

A multiscale density functional theory-quantum mechanics/molecular mechanics (DFT-QM/MM) scheme is presented, based on an efficient electrostatic coupling between the electronic density obtained from a grid-based projector augmented wave (GPAW) implementation of density functional theory and a classical potential energy function. The scheme is implemented in a general fashion and can be used with various choices for the descriptions of the QM or MM regions. Tests on H 2 O clusters, ranging from dimer to decamer show that no systematic energy errors are introduced by the coupling that exceeds the differences in the QM and MM descriptions. Over 1 ns of liquid water, Born-Oppenheimer QM/MM molecular dynamics (MD) are sampled combining 10 parallel simulations, showing consistent liquid water structure over the QM/MM border. The method is applied in extensive parallel MD simulations of an aqueous solution of the diplatinum [Pt 2 (P 2 O 5 H 2 ) 4 ] 4- complex (PtPOP), spanning a total time period of roughly half a nanosecond. An average Pt-Pt distance deviating only 0.01 Å from experimental results, and a ground-state Pt-Pt oscillation frequency deviating by <2% from experimental results were obtained. The simulations highlight a remarkable harmonicity of the Pt-Pt oscillation, while also showing clear signs of Pt-H hydrogen bonding and directional coordination of water molecules along the Pt-Pt axis of the complex.

Ultrafast X-ray absorption spectroscopy is applied to study the conversion of longitudinal to transverse phonons in aqueous solution. Permanganate solutes serve as X-ray probe molecules that permit the measurement of the conversion of 13.5 GHz, longitudinal phonons to 27 GHz, transverse phonons that propagate with high-frequency sound speed. The experimental results, combined with QM/MM MD simulations, show that the hydrogen bond network around the charged solutes has a glass-like stiffness that persists for at least tens of picoseconds.

Modern pulsed X-ray sources permit time-dependent measurements of dynamical changes in atoms and molecules via non-resonant scattering. The planning, analysis, and interpretation of such experiments, however, require a firm and elaborated theoretical framework. This paper provides a detailed description of time-resolved X-ray scattering by non-stationary electronic wave packets in atomic systems. A consistent application of the Waller-Hartree approximation is discussed and different contributions to the total differential scattering signal are identified and interpreted. Moreover, it is demonstrated how the scattering signal of wave packets in the hydrogen atom can be expressed analytically. This permits simulations without numerical integration and establishes a benchmark for both efficiency and accuracy. Based on that, scattering patterns of an exemplary wave packet in the hydrogen atom are computed for different points in time. In doing so, distinct features of time-resolved X-ray scattering by non-stationary electronic wave packets are illustrated and accentuated in greater detail than it has been done before.

The synthetic utility and theoretical basis of a photolabile hydroxylamine-linker are presented. The developed protocols enable the efficient synthesis and chemoselective photolytic release of either hydroxamates or carboxamides from solid support. The bidetachable mode of the linker unit is uniquely dependent on the solvent. Hydroxamic acids are obtained by performing photolysis in protic solvents, whereas photolysis in aprotic solvents enables the selective release of carboxamides.

Ultrafast pump-probe spectroscopy within the X-ray regime is now possible owing to the development of X-ray Free Electrons Lasers (X-FELs) and is opening new opportunities for the direct probing of femtosecond evolution of the nuclei, the electronic and spin degrees of freedom. In this contribution we use wavepacket dynamics of the photoexcited decay of a new Fe(ii) complex, [Fe(bmip) 2 ] 2+ (bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)pyridine), to simulate the experimental observables associated with femtosecond Fe K-edge X-ray Absorption Near-Edge Structure (XANES) and X-ray emission (XES) spectroscopy. We show how the evolution of the nuclear wavepacket is translated into the spectroscopic signal and the sensitivity of these approaches for following excited state dynamics.

The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2 (dimen) 4 ] 2+ , where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute-solvent pair distribution function, enabling the solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis.

This work provides a detailed mechanism for electron transfer in a heterodinuclear complex designed as a model system in which to study homogeneous molecular photocatalysis. With efficient Born-Oppenheimer molecular dynamics simulations, we show how intermediate, charge-separated states can mediate the electron transfer. We observe how Jahn-Teller distortion effects play out in solution, when the molecule has energetically close-lying states, and how this distortion is averaged out in the thermal sampling. Finally, we demonstrate how the solvent helps stabilize and localize the separated charge. The information on the electronic configuration and separate states is of key importance for designing next-generation photocatalysts.

Pyrazolate-bridged dinuclear Pt(II) complexes represent a series of molecules with tunable absorption and emission properties that can be directly modulated by structural factors, such as the Pt-Pt distance. However, direct experimental information regarding the structure of the emissive triplet excited state has remained scarce. Using time-resolved wide-angle X-ray scattering (WAXS), the excited triplet state molecular structure of [Pt(ppy)(μ-t-Bu2pz)]2 (ppy = 2-phenylpyridine; t-Bu2pz = 3,5-di-tert-butylpyrazolate), complex 1, was obtained in a dilute (0.5 mM) toluene solution utilizing the monochromatic X-ray pulses at Beamline 11IDD of the Advanced Photon Source. The excited-state structural analysis of 1 was performed based on the results from both transient WAXS measurements and density functional theory calculations to shed light on the primary structural changes in its triplet metal-metal-to-ligand charge-transfer (MMLCT) state, in particular, the Pt-Pt distance and ligand rotation. We found a pronounced Pt-Pt distance contraction accompanied by rotational motions of ppy ligands toward one another in the MMLCT state of 1. Our results suggest that the contraction is larger than what has previously been reported, but they are in good agreement with recent theoretical efforts and suggest the ppy moieties as targets for rational synthesis aimed at tuning the excited-state structure and properties.

We study the structural dynamics of photoexcited [Co(terpy)&#95;{2}]^{2+} in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ∼7  ps.