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1. Adjoint sensitivity kernels for free oscillation spectra

   https://doi.org/10.1093/gji/ggae136  

   Adourian, S.; Dursun, M_S; Lau, H_C_P; Al-Attar, D. (April 2024, Geophysical Journal International)

   SUMMARY We apply the adjoint method to efficiently calculate sensitivity kernels for long-period seismic spectra with respect to structural and source parameters. Our approach is built around the solution of the frequency-domain equations of motion using the direct solution method (DSM). The DSM is currently applied within large-scale mode coupling calculations and is also likely to be useful within finite-element type methods for modelling seismic spectra that are being actively developed. Using mode coupling theory as a framework for solving both the forward and adjoint equations, we present numerical examples that focus on the spectrum close to four eigenfrequencies (the low-frequency mode, 0S2, and higher frequency modes, namely 2S2, 0S7 and 0S10 for comparison). For each chosen observable, we plot sensitivity kernels with respect to 3-D perturbations in density and seismic wave speeds. We also use the adjoint method to calculate derivatives of observables with respect to the matrices occurring within mode coupling calculations. This latter approach points towards a generalization of the two-stage splitting function method for structural inversions that does not rely on inaccurate self-coupling or group-coupling approximations. Finally, we verify through direct calculation that our sensitivity kernels correctly predict the linear dependence of the chosen observables on model perturbations. In doing this, we highlight the importance of non-linearity within inversions of long-period spectra. 

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2. Origins of the diffuse shared proton vibrational signatures in proton-coupled electron transfer model dyad complexes

   https://doi.org/10.1063/5.0122777  

   Chen, Liangyi; Ma, Zifan; Fournier, Joseph A. (October 2022, The Journal of Chemical Physics)

   Phenol-benzimidazole and phenol-pyridine dyad complexes have served as popular model systems for the study of proton-coupled electron transfer (PCET) kinetics in solution-phase experiments. Interpretation of measured PCET rates in terms of key structural parameters, such as the H-bond donor–acceptor distance, however, remains challenging. Herein, we report vibrational spectra in the electronic ground state for a series of phenol-benzimidazole and phenol-pyridine complexes isolated and cryogenically cooled in an ion trap. The four models studied each display highly red-shifted and broadened OH stretching transitions that arise from strong H-bonding interactions between the phenol OH group and the basic N site on benzimidazole/pyridine rings. The OH stretch transition in each model displays relatively strong absorption onsets near 2500 cm −1 with broad shoulders that extend asymmetrically to higher frequencies over hundreds of wavenumbers. In contrast, the deuterated isotopologues yield much weaker OD stretch transitions that appear symmetrically broadened. The spectral breadth and shape of the OD stretch transitions are ascribed to variations in OD stretch frequencies that arise from zero-point distributions in the proton donor–acceptor low-frequency soft mode vibration. The asymmetric structure of the OH stretch transitions is attributed to a set of combination bands between the OH stretch and a series of low-frequency H-bond soft modes. The spectra and modeling highlight the importance of OH stretch-soft mode couplings, which are thought to play important roles in PCET and proton transfer dynamics. 

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3. Cooperative origin of proton pair diffusivity in yttrium substituted barium zirconate

   https://doi.org/10.1038/s42005-020-00464-5  

   Du, Peng; Chen, Qianli; Fan, Zhijun; Pan, Huizhu; Haibach, Frederick G.; Gomez, Maria A.; Braun, Artur (December 2020, Communications Physics)

   null (Ed.)

   Abstract Proton conduction is an important property for fuel cell electrolytes. The search for molecular details on proton transport is an ongoing quest. Here, we show that in hydrated yttrium doped barium zirconate using X-ray and neutron diffraction that protons tend to localize near the dopant yttrium as a conjugated superstructure. The proton jump time measured using quasi-elastic neutron scattering follows the Holstein-Samgin polaron model, revealing that proton hopping is weakly coupled to the high-frequency O-H stretching motion, but strongly coupled to low-frequency lattice phonons. The ratio of the proton polaron effective mass, m * , and the proton mass is m * / m  = 2, when coupled to the Zr-O stretching mode, giving experimental evidence of proton pairing in perovskites, as a result of proton-phonon coupling. Possible pathways of a proton pair are provided through Nudge Elastic Band calculations. The pairing of protons, when jumping, is discussed in context of a cooperative protonic charge transport process. 

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4. Experimental two-dimensional infrared spectra of methyl thiocyanate in water and organic solvents

   https://doi.org/10.1063/5.0190343  

   Shirley, Joseph C; Baiz, Carlos R (March 2024, The Journal of Chemical Physics)

   Thiocyanates, nitriles, and azides represent a versatile set of vibrational probes to measure the structure and dynamics in biological systems. The probes are minimally perturbative, the nitrile stretching mode appears in an otherwise uncongested spectral region, and the spectra report on the local environment around the probe. Nitrile frequencies and lineshapes, however, are difficult to interpret, and theoretical models that connect local environments with vibrational frequencies are often necessary. However, the development of both more accurate and intuitive models remains a challenge for the community. The present work provides an experimentally consistent collection of experimental measurements, including IR absorption and ultrafast two-dimensional infrared (2D IR) spectra, to serve as a benchmark in the development of future models. Specifically, we catalog spectra of the nitrile stretching mode of methyl thiocyanate (MeSCN) in fourteen different solvents, including non-polar, polar, and protic solvents. Absorption spectra indicate that π-interactions may be responsible for the line shape differences observed between aromatic and aliphatic alcohols. We also demonstrate that a recent Kamlet–Taft formulation describes the center frequency MeSCN. Furthermore, we report cryogenic infrared spectra that may lead to insights into the peak asymmetry in aprotic solvents. 2D IR spectra measured in protic solvents serve to connect hydrogen bonding with static inhomogeneity. We expect that these insights, along with the publicly available dataset, will be useful to continue advancing future models capable of quantitatively describing the relation between local environments, line shapes, and dynamics in nitrile probes. 

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5. Transition to strong coupling regime in hybrid plasmonic systems: Exciton-induced transparency and Fano interference

   Shahbazyan, Tigran V. (January 2021, arXiv)

   null (Ed.)

   We present a microscopic model describing the transition to strong coupling regime for an emitter resonantly coupled to a surface plasmon in a metal-dielectric structure. We demonstrate that the shape of scattering spectra is determined by an interplay of two distinct mechanisms. First is the near-field coupling between the emitter and the plasmon mode which underpins energy exchange between the system components and gives rise to exciton-induced transparency minimum in scattering spectra prior the transition to strong coupling regime. The second mechanism is Fano interference between the plasmon dipole and the plasmon-induced emitter's dipole as the system interacts with the radiation field. We show that the Fano interference can strongly affect the overall shape of scattering spectra, leading to the inversion of spectral asymmetry that was recently reported in the experiment. 

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