Electronic spectra of polyatomic molecules with resolved individual rotational transitions

The density of rotational transitions for a polyatomic molecule is so large that in general many such transitions are hidden under the Doppler profile, this being a fundamental limit of conventional high resolution electronic spectroscopy. We present here the first Doppler-free cw two-photon spectrum of a polyatomic molecule. In the case of benzene, 400 lines are observed of which 300 are due to single rotational transitions, their spacing being weil below the Doppler profile. The resolution so achieved is 1.5 X 10'. Benzene is a prototype planar molecule taken to have D •• symmetry in the ground as weil as in the first excited state. From our ultra-high resolution results it is found that benzene in the excited SI state i8 a symmetrical rotor to a high degree. A negative inertial defect is found for the excited state. The origin of this inertial defect is discused

Global dynamics above the ground state for the nonlinear Klein-Gordon equation without a radial assumption

We extend our previous result on the focusing cubic Klein-Gordon equation in three dimensions to the non-radial case, giving a complete classification of global dynamics of all solutions with energy at most slightly above that of the ground state.Comment: 40 page

Back to the roots of "channel three"

Rotationally resolved fluorescence excitation and resonance enhanced multiphoton ionization (MPI) spectra of the 610130 one-photon band of benzene at the onset of ``channel three'' are reported. The fluorescence decay is monitored after rotationally selected excitation and a large variation of the nonradiative decay time (<1 to 6.8 ns) is found for the different rotational states at the vibrational excess energy of 3287 cm−1 in S1. The rotational structure of the fluorescence excitation spectrum and the MPI spectrum measured with delayed laser pulses differ considerably. All observed lines of the MPI spectrum were assigned and the rotational line structure can only be understood with a model which incorporates interference between different decay channels. Due to this interference, particular rotational states decay fairly slowly and give rise to lines in the spectrum while states with neighboring rotational quantum numbers decay rapidly and are therefore not found in the spectrum. The previously reported drastic increase of the electronic, nonradiative decay of benzene in this region of excess energy, which led to the postulation of ``channel three,'' cannot be confirmed. Instead, the optically excited rovibronic states are thought to be coupled to background states within S1 which are themselves broadened due to strong coupling to the highly excited S0 electronic state rather than due to an unknown (``channel three'') or isomerization process. The Journal of Chemical Physics is copyrighted by The American Institute of Physics

A network model to investigate structural and electrical properties of proteins

One of the main trend in to date research and development is the miniaturization of electronic devices. In this perspective, integrated nanodevices based on proteins or biomolecules are attracting a major interest. In fact, it has been shown that proteins like bacteriorhodopsin and azurin, manifest electrical properties which are promising for the development of active components in the field of molecular electronics. Here we focus on two relevant kinds of proteins: The bovine rhodopsin, prototype of GPCR protein, and the enzyme acetylcholinesterase (AChE), whose inhibition is one of the most qualified treatments of Alzheimer disease. Both these proteins exert their functioning starting with a conformational change of their native structure. Our guess is that such a change should be accompanied with a detectable variation of their electrical properties. To investigate this conjecture, we present an impedance network model of proteins, able to estimate the different electrical response associated with the different configurations. The model resolution of the electrical response is found able to monitor the structure and the conformational change of the given protein. In this respect, rhodopsin exhibits a better differential response than AChE. This result gives room to different interpretations of the degree of conformational change and in particular supports a recent hypothesis on the existence of a mixed state already in the native configuration of the protein.Comment: 25 pages, 12 figure

Surgical therapy of celiac axis and superior mesenteric artery syndrome

INTRODUCTION Compression syndromes of the celiac artery (CAS) or superior mesenteric artery (SMAS) are rare conditions that are difficult to diagnose; optimal treatment remains complex, and symptoms often persist after surgery. We aim to review the literature on surgical treatment and postoperative outcome in CAS and SMAS syndrome. METHODS A systematic literature review of medical literature databases on the surgical treatment of CAS and SMAS syndrome was performed from 2000 to 2022. Articles were included according to PROSPERO guidelines. The primary endpoint was the failure-to-treat rate, defined as persistence of symptoms at first follow-up. RESULTS Twenty-three studies on CAS (n = 548) and 11 on SMAS (n = 168) undergoing surgery were included. Failure-to-treat rate was 28% for CAS and 21% for SMAS. Intraoperative blood loss was 95 ml (0-217) and 31 ml (21-50), respectively, and conversion rate was 4% in CAS patients and 0% for SMAS. Major postoperative morbidity was 2% for each group, and mortality was described in 0% of CAS and 0.4% of SMAS patients. Median length of stay was 3 days (1-12) for CAS and 5 days (1-10) for SMAS patients. Consequently, 47% of CAS and 5% of SMAS patients underwent subsequent interventions for persisting symptoms. CONCLUSION Failure of surgical treatment was observed in up to every forth patient with a high rate of subsequent interventions. A thorough preoperative work-up with a careful patient selection is of paramount importance. Nevertheless, the surgical procedure was associated with a beneficial risk profile and can be performed minimally invasive

On the spectral properties of L_{+-} in three dimensions

This paper is part of the radial asymptotic stability analysis of the ground state soliton for either the cubic nonlinear Schrodinger or Klein-Gordon equations in three dimensions. We demonstrate by a rigorous method that the linearized scalar operators which arise in this setting, traditionally denoted by L_{+-}, satisfy the gap property, at least over the radial functions. This means that the interval (0,1] does not contain any eigenvalues of L_{+-} and that the threshold 1 is neither an eigenvalue nor a resonance. The gap property is required in order to prove scattering to the ground states for solutions starting on the center-stable manifold associated with these states. This paper therefore provides the final installment in the proof of this scattering property for the cubic Klein-Gordon and Schrodinger equations in the radial case, see the recent theory of Nakanishi and the third author, as well as the earlier work of the third author and Beceanu on NLS. The method developed here is quite general, and applicable to other spectral problems which arise in the theory of nonlinear equations

Spectral Analysis for Matrix Hamiltonian Operators

In this work, we study the spectral properties of matrix Hamiltonians generated by linearizing the nonlinear Schr\"odinger equation about soliton solutions. By a numerically assisted proof, we show that there are no embedded eigenvalues for the three dimensional cubic equation. Though we focus on a proof of the 3d cubic problem, this work presents a new algorithm for verifying certain spectral properties needed to study soliton stability. Source code for verification of our comptuations, and for further experimentation, are available at http://www.math.toronto.edu/simpson/files/spec_prop_code.tgz.Comment: 57 pages, 22 figures, typos fixe

Biases in the perceived timing of perisaccadic perceptual and motor events

Subjects typically experience the temporal interval immediately following a saccade as longer than a comparable control interval. One explanation of this effect is that the brain antedates the perceptual onset of a saccade target to around the time of saccade initiation. This could explain the apparent continuity of visual perception across eye movements. Thisantedating account was tested in three experiments in which subjects made saccades of differing extents and then judged either the duration or the temporal order of key events. Postsaccadic stimuli underwent subjective temporal lengthening and had early perceived onsets. A temporally advanced awareness of saccade completion was also found, independently of antedating effects. These results provide convergent evidence supporting antedating and differentiating it from other temporal biases