Quantum monodromy in NCNCS - direct experimental confirmation.

Since the first confirmation of quantum monodromy in NCNCS (B. P. Winnewisser et al., Report No. TH07 in 60th International Symposium on Molecular Spectroscopy, Columbus, OH, (2005) and B. P. Winnewisser et al., Phys. Rev. Lett., 2005, 95, 243002) we have continued to explore its implications for the quantum structure of molecules. To confirm quantum monodromy bending-vibrational + axial-rotational quantum energy level information is needed. This was not directly available from the pure a-type rotational transitions available in 2005. The confirmation of quantum monodromy therefore had to be based on the fitting of the Generalised SemiRigid Bender (GSRB) model to the experimental rotational data. The GSRB is a physically motivated model and was able to extract the required information based on the changes of the rotational energy level structure upon excitation of the bending vibration and of the axial rotation. These results were, in some sense, predictions. Our goal here was to obtain a fully experimental and unambigous confirmation of quantum monodromy in NCNCS. This involved a series of experimental campaigns at the Canadian Light Source (CLS) synchrotron. To coax the required information out of the masses of spectral data that had been obtained a variety of techniques had to be used. The result is that we can now confirm, without recourse to a theoretical model, the existence of quantum monodromy in the ν7 bending mode of NCNCS. As a side benefit we also confirm the power of the GSRB model to extract the required information from the previously available data. The predictions previously provided by the GSRB were surprisingly accurate. Only a slight augmentation of the model was required to allow us to refit it including the new data, while maintaining the quality of the fitting for that data previously available. We also present a very basic introduction to the idea of monodromy and to how the GSRB was used.

Improving Access to Tertiary Movement Disorders Subspecialty Care: A Team Model Born From the COVID-19 Crisis.

Patient demand continues to outpace growth of the neurology workforce, especially in its subspecialties such as movement disorders. Various strategies have been deployed to address this. The coronavirus disease 2019 pandemic accentuated the mismatch by propelling telemedicine and access demands to the forefront. Previously, we reported improving general neurology access using a physician-advanced practice provider team model. Here, we share our experiences of piloting a similar model in subspecialty care (movement disorders) between September 1 and December 17, 2020. Before the pilot, the wait time to be seen by movement disorders subspecialists exceeded 4 months. Our data show marked improvement in new patient access (23.8% improvement and 214% increase in the number of new patients seen) with excellent patient acceptance. Our approach and the lessons learned may be useful to address access for other neurology subspecialties.

Pursuit of quantum monodromy in the far-infrared and mid-infrared spectra of NCNCS using synchrotron radiation.

Quantum monodromy has a dramatic and defining impact on all those physical properties of chain-molecules that depend on a large-amplitude bending coordinate, including in particular the distribution of the ro-vibrational energy levels. As revealed by its pure rotational (a-type) spectrum [B. P. Winnewisser et al., Phys. Chem. Chem. Phys., 2010, 12, 8158-8189] cyanogen iso-thiocyanate, NCNCS, is a particularly illuminating exemplar of quantum monodromy: it clearly shows the distinctive monodromy-induced dislocation of the ro-vibrational energy level pattern for its low-lying bending mode. This dislocation centers on a lattice defect in the energy vs. momentum map of the ro-vibrational levels at the top of the barrier to linearity, and represents an example of an excited state quantum phase transition [D. Larese and F. Iachello, J. Mol. Struct., 2011, 1006, 611-628]. To complete the data, so far limited to ΔJ = +1 transitions, we decided to measure the high-resolution far-infrared band of the large-amplitude bending vibration ν7, and, if possible, mid-infrared bands. This Perspectives article presents our ongoing progress towards this goal, beginning with the description of how to predict line positions and intensities of the a- and b-type bands of the large amplitude bending mode using the Generalized-SemiRigid-Bender (GSRB) Hamiltonian for NCNCS and ab initio dipole moment functions [B. P. Winnewisser et al., Phys. Chem. Chem. Phys., 2010, 12, 8158-8189]. We include background information about synchrotron physics to clarify the advantages and limitations of that radiation source for our experiments. Details of the chemical preparation and sample handling, leading to the realization that NCNCS is 50 kJ mol(-1) lower in energy than its isomer S(CN)2 [Z. Kisiel et al., J. Phys. Chem. A, 2013, 117, 13815-13824] are included. We present the far-infrared and mid-infrared spectrum of NCNCS obtained at the Canadian Light Source synchrotron, using the IFS 125HR Bruker Fourier transform spectrometer. Eight of the fundamental vibrational modes of NCNCS have now been observed at high resolution. Initial analyses of the data confirm band assignments and demonstrate the accuracy of the predictions.

An option for improving access to outpatient general neurology.

Creating a team of nurse practitioner/physician assistant providers with a supervising physician is one potential model to extend limited physician resources for those medical specialties such as neurology, whose outpatient access is suboptimal. We offered new patient appointments with the access team. Monthly lead time (time to third available appointment) revealed that overall new-patient access improved from an average time-to-appointment wait of 299 days down to 10 days. Patients completed an anonymous satisfaction survey about providers before and after the launch of the new access team; the results demonstrated preserved patient satisfaction with providers in this new team-based model.

Laser induced amplified spontaneous emission from the f 0(g)(+) (3P0) ion-pair state of I2.

Laser induced amplified spontaneous emission (ASE) from the f 0g (+) ((3)P0) (vf = 1-7) ion-pair state of I2 was directly observed using an optical-optical double resonance technique with the B 0u (+) (vB = 21) valence state as the intermediate state. The emission detected at ~1660 nm was assigned to transitions from the f 0g (+) state to the D 0u (+) ((3)P2) ion-pair state. The transitions observed in the dispersed IR emission spectra were found to be between vibrational levels having the same vibrational quantum numbers in both electronic states, vf = vD. This is due to the almost parallel nature of the potential energy functions of the f 0g (+) and D 0u (+) states, leading to almost unit values for the Franck-Condon factors for vf = vD. That the observed infrared emission is due to ASE is shown by the facts that it propagated in a limited range of solid angles, exhibited a clear threshold against the input-laser power, and had different polarization to that of laser induced fluorescence.

Symbiotic bacteria induced necrotizing pancreatitis.

CONTEXT: Intestinal flora and anaerobes are frequently implicated in causing infectious necrotizing pancreatitis however Bifidobacterium and Veillonella have rarely been isolated as the causative agents. Bifidobacterium and Veillonella are commensal anaerobes which reside in gastrointestinal tract and help deconjugate bile acids. Bifidobacterium is also frequently used in probiotics. CASE REPORT: We present a 68-year-old man who initially presented with gallstone pancreatitis but eventually developed Bifidobacterium and Veillonella species induced necrotizing pancreatitis and pseudocyst formation. CONCLUSION: Under rare circumstances commensal gut flora can turn pathogenic which can lead to life-threatening morbidity and may even result in mortality.

Torsion-rotation coupling and the determination of the torsional potential energy function of HSOH.

Hindered torsional motion in a molecule such as HSOH leads to tunnelling splittings. Lying between the simpler limiting cases of strongly hindered torsion (the "we can simply neglect the tunnelling" limit) and that of free internal rotation (the "tunnelling pair of levels are just different vibrational states" limit) HSOH is particularly challenging due to strong and inherent torsion-rotation coupling. The low symmetry due to the different terminal moieties, SH and OH, further enriches the energy level pattern by allowing a systematic mixing within each quadruplet of torsion- and asymmetry-doubled levels. This mixing, which varies in a systematic manner with angular momentum quantum numbers, can reach 50% and is in addition to the mass-dependent and quasicyclic variation of the tunnelling splittings. We show that a carefully implemented reduced-dimension model, the Generalised SemiRigid Bender (GSRB), combined with a few modest ab initio calculations, is sufficient to account for the bulk of these physical effects. We also point out the reversal of energy pairing of torsional levels with increased energy. That is, at low torsional energy the lowest of the torsional level pair is the symmetric level while at high torsional energy it is the antisymmetric level which is the lowest. Finally, we present a purely empirical determination of the tunnelling splittings for K = 0, 1, 3, 4, and 5.

Analysis of the FASSST rotational spectrum of NCNCS in view of quantum monodromy.

Quantum monodromy has a strong impact on the ro-vibrational energy levels of chain molecules whose bending potential energy function has the form of the bottom of a champagne bottle (i.e. with a hump or punt) around the linear configuration. NCNCS, cyanogen iso-thiocyanate, is a particularly good example of such a molecule and clearly exhibits a distinctive monodromy-induced dislocation of the energy level pattern at the bending-rotation energy at the top of the potential energy hump. Indeed, NCNCS [B. P. Winnewisser et al., Phys. Rev. Lett. 2005, 95, 243002] and the water molecule [N. F. Zobov et al., Chem. Phys. Lett. 2005, 414, 193-197] were the first two molecules for which experimental confirmation of quantum monodromy was obtained. We used the fast scan sub-millimetre spectroscopic technique (FASSST) to extend the measurements and spectral analysis to pure rotational transitions (end-over-end) in bending vibrational states lying well above the monodromy point. The analysis of 9204 lines assigned to 7 vibrational states, presented here, shows that the topological properties of the bending potential function are mapped onto every aspect of the ro-vibrational energy levels involving excitation of the quasi-linear bending vibration. In order to model the large amplitude dynamics of such a molecular system, and also to achieve some insight beyond satisfactory parameters for reproducing the spectrum, we used the generalized semi-rigid bender (GSRB) Hamiltonian, which is described in some detail. This Hamiltonian provides a good description of the energy levels over the seven bending states observed, coming close to experimental accuracy. Due to high J values of the measured rotational transitions (J

Moxifloxacin induced fatal hepatotoxicity in a 72-year-old man: a case report.

Moxifloxacin is a newer-generation synthetic fluoroquinolone that is used for treatment of acute bacterial sinusitis, acute exacerbation of chronic bronchitis, community acquired pneumonia, intra-abdominal infections and skin/skin structure infections. We describe a case of fatal hepatotoxicity caused by Moxifloxacin in a 72-year-old man. He presented with jaundice and epigastric tenderness that started one week after being treated for acute exacerbation of his chronic bronchitis with Moxifloxacin by his primary care physician. He was admitted to intensive care unit for close monitoring. His labs showed marked elevation in liver enzymes and bilirubin. His condition continued to deteriorate in intensive care unit despite supportive care. Acute hepatic failure which resulted in his death was attributed to idiosyncratic reaction to Moxifloxacin.

Energy level promotion in the correlation from the tunnelling-doubled harmonic oscillator to the bi-rotor: application to internal rotation in molecules.

A surprisingly rich variety of phenomena are revealed in the energy level correlation between the limits of a tunnelling doubled harmonic oscillator and a bi-rotor. Some levels are found to have their vibrational quantum number "promoted" upon removal of the barrier to rotation, other levels, which we dub "invariant", are found to be completely independent of the barrier, while yet other levels exhibit a smooth transition between these limits. The general nature of these features can be understood in terms of the different degeneracies of the limiting cases. The elucidation of these effects aids the understanding of the rotational-vibrational energy levels of molecules having two internal rotor moieties.

Decay dynamics of the long-range H1Sigmag+ state of D2 and H2: experiment and theory.

We present accurate experimental measurements of the lifetimes of rovibrational levels of the long-range H1Sigmag+ state for both D2 and H2, obtained directly from the observation of the time-dependent decay of the fluorescence from these excited levels. These results improve upon and extend those of Reinhold et al. [J. Chem. Phys. 112, 10754 (2000)]. Several decay pathways are open to these levels including fluorescence, predissociation, and autoionization. We present theoretical results for each of these processes, each calculated using the simplest but still appropriate level of theory. In particular, the theoretical calculations provide a quantitative explanation of the dramatic vibrational dependence of the observed lifetimes, the isotope dependence of the lifetimes for levels well localized within the H potential well and therefore not subject to significant tunneling, and an insight into the role of enhanced tunneling in autoionization. In these calculations each of the rovibrational levels of the H state is treated individually, without having to engage in a global coupled-state calculation.

Experimental confirmation of quantum monodromy: the millimeter wave spectrum of cyanogen isothiocyanate NCNCS.

We have made energy-momentum maps for the experimental end-over-end rotational energy and the two-dimensional bending vibrational energy, both of which confirm the dominating effects of nontrivial quantum monodromy in cyanogen isothiocyanate. Accidental resonances in the rotational spectra yield accurate intervals between bending states.