875 research outputs found
A theory of nonvertical triplet energy transfer in terms of accurate potential energy surfaces: The transfer reaction from π,π∗ triplet donors to 1,3,5,7-cyclooctatetraene
Triplet energy transfer (TET) from aromatic donors to 1,3,5,7-cyclooctatetraene (COT) is an extreme case of “nonvertical” behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated (Arrhenius) process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces (PES) of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion parameter γ = (2g2/κ1)1/2 in which g stands for the norm of the energy gradient in the PES of the acceptor triplet state and κ1 is a combination of vibrational force constants of the ground-state acceptor in the gradient direction. The application of the model to existing experimental data for the triplet energy transfer reaction to COT from a series of π,π∗ triplet donors, provides a detailed interpretation of the parameters that determine the transfer rate constant. In addition, the model shows that the observed decrease of the acceptor electronic excitation energy is due to thermal activation of C�C bond stretchings and C–C bond torsions, which collectively change the ground-state COT bent conformation (D2d) toward a planar triplet state (D8h)[email protected]
Selective Reflection Spectroscopy at the Interface between a Calcium Fluoride Window and Cs Vapour
A special vapour cell has been built, that allows the measurement of the
atom-surface van der Waals interaction exerted by a CaF2 window at the
interface with Cs vapour. Mechanical and thermal fragility of fluoride windows
make common designs of vapour cells unpractical, so that we have developed an
all-sapphire sealed cell with an internal CaF2 window. Although impurities were
accidentally introduced when filling-up the prototype cell, leading to a
line-broadening and shift, the selective reflection spectrum on the Cs D1 line
(894 nm) makes apparent the weak van der Waals surface interaction. The
uncertainties introduced by the effects of these impurities in the van der
Waals measurement are nearly eliminated when comparing the selective reflection
signal at the CaF2 interface of interest, and at a sapphire window of the same
cell. The ratio of the interaction respectively exerted by a sapphire interface
and a CaF2 interface is found to be 0.55 0.25, in good agreement with the
theoretical evaluation of ~0.67.Comment: soumis \`a Appl Phys B MS 4734
Parametric localized modes in quadratic nonlinear photonic structures
We analyze two-color spatially localized modes formed by parametrically
coupled fundamental and second-harmonic fields excited at quadratic (or chi-2)
nonlinear interfaces embedded into a linear layered structure --- a
quasi-one-dimensional quadratic nonlinear photonic crystal. For a periodic
lattice of nonlinear interfaces, we derive an effective discrete model for the
amplitudes of the fundamental and second-harmonic waves at the interfaces (the
so-called discrete chi-2 equations), and find, numerically and analytically,
the spatially localized solutions --- discrete gap solitons. For a single
nonlinear interface in a linear superlattice, we study the properties of
two-color localized modes, and describe both similarities and differences with
quadratic solitons in homogeneous media.Comment: 9 pages, 8 figure
p75 neurotrophin receptor regulates energy balance in obesity
Obesity and metabolic syndrome reflect the dysregulation of molecular pathways that control energy homeostasis. Here, we show that the p75 neurotrophin receptor (p75NTR) controls energy expenditure in obese mice on a high-fat diet (HFD). Despite no changes in food intake, p75NTR-null mice were protected from HFD-induced obesity and remained lean as a result of increased energy expenditure without developing insulin resistance or liver steatosis. p75NTR directly interacts with the catalytic subunit of protein kinase A (PKA) and regulates cAMP signaling in adipocytes, leading to decreased lipolysis and thermogenesis. Adipocyte-specific depletion of p75NTR or transplantation of p75NTR-null white adipose tissue (WAT) into wild-type mice fed a HFD protected against weight gain and insulin resistance. Our results reveal that signaling from p75NTR to cAMP/PKA regulates energy balance and suggest that non-CNS neurotrophin receptor signaling could be a target for treating obesity and the metabolic syndrome
Exploring the van der Waals Atom-Surface attraction in the nanometric range
The van der Waals atom-surface attraction, scaling as C3 z-3 for z the
atom-surface distance, is expected to be valid in the distance range 1-1000 nm,
covering 8-10 orders of magnitudes in the interaction energy. A Cs vapour
nanocell allows us to analyze the spectroscopic modifications induced by the
atom-surface attraction on the 6P3/2->6D5/2 transition. The measured C3 value
is found to be independent of the thickness in the explored range 40-130 nm,
and is in agreement with an elementary theoretical prediction. We also discuss
the specific interest of exploring short distances and large interaction
energy.Comment: to appear in Europhysics Letter
Selective Reflection Spectroscopy on the UV Third Resonance Line of Cs : Simultaneous Probing of a van der Waals Atom-Surface Interaction Sensitive to Far IR Couplings and of Interatomic Collisions
We report on the analysis of FM selective reflection experiments on the
6S1/2->8P3/2 transition of Cs at 388 nm, and on the measurement of the surface
van der Waals interaction exerted by a sapphire interface on Cs(8P3/2). Various
improvements in the systematic fitting of the experiments have permitted to
supersede the major difficulty of a severe overlap of the hyperfine components,
originating on the one hand in a relatively small natural structure, and on the
other hand on a large pressure broadening imposed by the high atomic density
needed for the observation of selective reflection on a weak transition. The
strength of the van der Waals surface interaction is evaluated to be 7310
kHz.m3. An evaluation of the pressure shift of the transition is also
provided as a by-product of the measurement. We finally discuss the
significance of an apparent disagreement between the experimental measurement
of the surface interaction, and the theoretical value calculated for an
electromagnetic vacuum at a null temperature. The possible influence of the
thermal excitation of the surface is evoked, because, the dominant
contributions to the vW interaction for Cs(8P3/2) lie in the far infrared
range.Comment: submitted to Laser Physics - issue in the memory of Herbert Walther
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