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1. Sub-Doppler infrared spectroscopy of resonance-stabilized hydrocarbon intermediates: ν ₃ / ν ₄ CH stretch modes and CH ₂ internal rotor dynamics of benzyl radical

   https://doi.org/10.1039/c7cp05776h  

   Kortyna, A.; Samin, A. J.; Miller, T. A.; Nesbitt, D. J. (January 2017, Physical Chemistry Chemical Physics)

   Highly reactive benzyl radicals are generated by electron dissociative attachment to benzyl chloride doped into a neon–hydrogen–helium discharge and immediately cooled to T rot = 15 K in a high density, supersonic slit expansion environment. The sub-Doppler spectra are fit to an asymmetric-top rotational Hamiltonian, thereby yielding spectroscopic constants for the ground ( v = 0) and first excited ( v = 1, ν 3 , ν 4 ) vibrational levels of the ground electronic state. The rotational constants obtained for the ground state are in good agreement with previous laser induced fluorescence measurements (LIF), with vibrational band origins ( ν 3 = 3073.2350 ± 0.0006 cm −1 , ν 4 = 3067.0576 ± 0.0006 cm −1 ) in agreement with anharmonically corrected density functional theory calculations. To assist in detection of benzyl radical in the interstellar medium, we have also significantly improved the precision of the ground state rotational constants through combined analysis of the ground state IR and LIF combination differences. Of dynamical interest, there is no evidence in the sub-Doppler spectra for tunneling splittings due to internal rotation of the CH 2 methylene subunit, which implies a significant rotational barrier consistent with partial double bond character in the CC bond. This is further confirmed with high level ab initio calculations at the CCSD(T)-f12b/ccpVdZ-f12 level, which predict a zero-point energy corrected barrier to internal rotation of Δ E tun ≈ 11.45 kcal mol −1 or 4005 cm −1 . In summary, the high-resolution infrared spectra are in excellent agreement with simple physical organic chemistry pictures of a strongly resonance-stabilized benzyl radical with a nearly rigid planar structure due to electron delocalization around the aromatic ring. 

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2. Electrically-driven robust tuning of lattice thermal conductivity

   https://doi.org/10.1039/d2cp01117d  

   Zhou, E; Wei, Donghai; Wu, Jing; Qin, Guangzhao; Hu, Ming (July 2022, Physical Chemistry Chemical Physics)

   The two-dimensional (2D) materials, represented by graphene, stand out in the electrical industry applications of the future and have been widely studied. As commonly existing in electronic devices, the electric field has been extensively utilized to modulate the performance. However, how the electric field regulates thermal transport is rarely studied. Herein, we investigate the modulation of thermal transport properties by applying an external electric field ranging from 0 to 0.4 V Å −1 , with bilayer graphene, monolayer silicene, and germanene as study cases. The monotonically decreasing trend of thermal conductivity in all three materials is revealed. A significant effect on the scattering rate is found to be responsible for the decreased thermal conductivity driven by the electric field. Further evidence shows that the reconstruction of internal electric field and generation of induced charges lead to increased scattering rate from strong phonon anharmonicity. Thus, the ultralow thermal conductivity emerges with the application of external electric fields. Applying an external electric field to regulate thermal conductivity illustrates a constructive idea for highly efficient thermal management. 

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3. Search for double-beta decay of $$\mathrm {^{130}Te}$$ to the $$0^+$$ states of $$\mathrm {^{130}Xe}$$ with CUORE

   https://doi.org/10.1140/epjc/s10052-021-09317-z  

   Adams, D. Q.; Alduino, C.; Alfonso, K.; Avignone, F. T.; Azzolini, O.; Bari, G.; Bellini, F.; Benato, G.; Biassoni, M.; Branca, A.; et al (July 2021, The European Physical Journal C)

   null (Ed.)

   Abstract The CUORE experiment is a large bolometric array searching for the lepton number violating neutrino-less double beta decay ( $$0\nu \beta \beta $$ 0 ν β β ) in the isotope $$\mathrm {^{130}Te}$$ 130 Te . In this work we present the latest results on two searches for the double beta decay (DBD) of $$\mathrm {^{130}Te}$$ 130 Te to the first $$0^{+}_2$$ 0 2 + excited state of $$\mathrm {^{130}Xe}$$ 130 Xe : the $$0\nu \beta \beta $$ 0 ν β β decay and the Standard Model-allowed two-neutrinos double beta decay ( $$2\nu \beta \beta $$ 2 ν β β ). Both searches are based on a 372.5 kg $$\times $$ × yr TeO $$_2$$ 2 exposure. The de-excitation gamma rays emitted by the excited Xe nucleus in the final state yield a unique signature, which can be searched for with low background by studying coincident events in two or more bolometers. The closely packed arrangement of the CUORE crystals constitutes a significant advantage in this regard. The median limit setting sensitivities at 90% Credible Interval (C.I.) of the given searches were estimated as $$\mathrm {S^{0\nu }_{1/2} = 5.6 \times 10^{24} \, \mathrm {yr}}$$ S 1 / 2 0 ν = 5.6 × 10 24 yr for the $${0\nu \beta \beta }$$ 0 ν β β decay and $$\mathrm {S^{2\nu }_{1/2} = 2.1 \times 10^{24} \, \mathrm {yr}}$$ S 1 / 2 2 ν = 2.1 × 10 24 yr for the $${2\nu \beta \beta }$$ 2 ν β β decay. No significant evidence for either of the decay modes was observed and a Bayesian lower bound at $$90\%$$ 90 % C.I. on the decay half lives is obtained as: $$\mathrm {(T_{1/2})^{0\nu }_{0^+_2} > 5.9 \times 10^{24} \, \mathrm {yr}}$$ ( T 1 / 2 ) 0 2 + 0 ν > 5.9 × 10 24 yr for the $$0\nu \beta \beta $$ 0 ν β β mode and $$\mathrm {(T_{1/2})^{2\nu }_{0^+_2} > 1.3 \times 10^{24} \, \mathrm {yr}}$$ ( T 1 / 2 ) 0 2 + 2 ν > 1.3 × 10 24 yr for the $$2\nu \beta \beta $$ 2 ν β β mode. These represent the most stringent limits on the DBD of $$^{130}$$ 130 Te to excited states and improve by a factor $$\sim 5$$ ∼ 5 the previous results on this process. 

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4. On the nature of hydrogen bonding in the H2S dimer

   https://doi.org/10.1038/s41467-024-53444-6  

   Jäger, Svenja; Khatri, Jai; Meyer, Philipp; Henkel, Stefan; Schwaab, Gerhard; Nandi, Apurba; Pandey, Priyanka; Barlow, Kayleigh R; Perkins, Morgan A; Tschumper, Gregory S; et al (December 2024, Nature Communications)

   Abstract Hydrogen bonding is a central concept in chemistry and biochemistry, and so it continues to attract intense study. Here, we examine hydrogen bonding in the H₂S dimer, in comparison with the well-studied water dimer, in unprecedented detail. We record a mass-selected IR spectrum of the H₂S dimer in superfluid helium nanodroplets. We are able to resolve a rotational substructure in each of the three distinct bands and, based on it, assign these to vibration-rotation-tunneling transitions of a single intramolecular vibration. With the use of high-level potential and dipole-moment surfaces we compute the vibration-rotation-tunneling dynamics and far-infrared spectrum with rigorous quantum methods. Intramolecular mode Vibrational Self-Consistent-Field and Configuration-Interaction calculations provide the frequencies and intensities of the four SH-stretch modes, with a focus on the most intense, the donor bound SH mode which yields the experimentally observed bands. We show that the intermolecular modes in the H₂S dimer are substantially more delocalized and more strongly mixed than in the water dimer. The less directional nature of the hydrogen bonding can be quantified in terms of weaker electrostatic and more important dispersion interactions. The present study reconciles all previous spectroscopic data, and serves as a sensitive test for the potential and dipole-moment surfaces. 

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5. Electric Mode Excitation in the Atmosphere by Magnetospheric Impulses and ULF Waves

   https://doi.org/10.3389/feart.2020.619227  

   Pilipenko, V. A.; Fedorov, E. N.; Martines-Bedenko, V. A.; Bering, E. A. (January 2021, Frontiers in Earth Science)

   null (Ed.)

   Variations of vertical atmospheric electric field E z have been attributed mainly to meteorological processes. On the other hand, the theory of electromagnetic waves in the atmosphere, between the bottom ionosphere and earth’s surface, predicts two modes, magnetic H (TE) and electric E (TH) modes, where the E-mode has a vertical electric field component, E z . Past attempts to find signatures of ULF (periods from fractions to tens of minutes) disturbances in E z gave contradictory results. Recently, study of ULF disturbances of atmospheric electric field became feasible thanks to project GLOCAEM, which united stations with 1 sec measurements of potential gradient. These data enable us to address the long-standing problem of the coupling between atmospheric electricity and space weather disturbances at ULF time scales. Also, we have reexamined results of earlier balloon-born electric field and ground magnetic field measurements in Antarctica. Transmission of storm sudden commencement (SSC) impulses to lower latitudes was often interpreted as excitation of the electric TH 0 mode, instantly propagating along the ionosphere–ground waveguide. According to this theoretical estimate, even a weak magnetic signature of the E-mode ∼1 nT must be accompanied by a burst of E z well exceeding the atmospheric potential gradient. We have examined simultaneous records of magnetometers and electric field-mills during >50 SSC events in 2007–2019 in search for signatures of E-mode. However, the observed E z disturbance never exceeded background fluctuations ∼10 V/m, much less than expected for the TH 0 mode. We constructed a model of the electromagnetic ULF response to an oscillating magnetospheric field-aligned current incident onto the realistic ionosphere and atmosphere. The model is based on numerical solution of the full-wave equations in the atmospheric-ionospheric collisional plasma, using parameters that were reconstructed using the IRI model. We have calculated the vertical and horizontal distributions of magnetic and electric fields of both H- and E-modes excited by magnetospheric field-aligned currents. The model predicts that the excitation rate of the E-mode by magnetospheric disturbances is low, so only a weak E z response with a magnitude of ∼several V/m will be produced by ∼100 nT geomagnetic disturbance. However, at balloon heights (∼30 km), electric field of the E-mode becomes dominating. Predicted amplitudes of horizontal electric field in the atmosphere induced by Pc5 pulsations and travelling convection vortices, about tens of mV/m, are in good agreement with balloon electric field and ground magnetometer observations. 

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