More Like this

1. Applying Unconventional Spectroscopies to the Single‐Molecule Magnets, Co(PPh 3 ) 2 X 2 (X=Cl, Br, I): Unveiling Magnetic Transitions and Spin‐Phonon Coupling

   https://doi.org/10.1002/chem.202100705  

   Bone, Alexandria N. ; Widener, Chelsea N. ; Moseley, Duncan H. ; Liu, Zhiming ; Lu, Zhengguang ; Cheng, Yongqiang ; Daemen, Luke L. ; Ozerov, Mykhaylo ; Telser, Joshua ; Thirunavukkuarasu, Komalavalli ; et al ( August 2021 , Chemistry – A European Journal)

   Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single‐molecule magnets (SMMs). Spin‐phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin‐phonon coupling in molecules is challenging. We have found that far‐IR magnetic spectra (FIRMS) of Co(PPh₃)₂X₂(Co‐X; X=Cl, Br, I) reveal rarely observed spin‐phonon coupling as avoided crossings between magnetic andu‐symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero‐field split (ZFS) levels of theS=3/2 electronic ground state were probed by INS, high‐frequency and ‐field EPR (HFEPR), FIRMS, and frequency‐domain FT terahertz EPR (FD‐FT THz‐EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) andgvalues. Ligand‐field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities inCo‐X, showing that the larger Co(II) spin density in a molecule, the larger its ZFS magnitude. The current work reveals dynamics of magnetic and phonon excitations in SMMs. Studies of such couplings in the future would help to understand how spin‐phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling.

    

   more » « less
2. Magnetic anisotropies and slow magnetic relaxation of three tetrahedral tetrakis(pseudohalido)–cobalt( ii ) complexes

   https://doi.org/10.1039/D1NJ01916C  

   Chen, Shu-Yang ; Lv, Wei ; Cui, Hui-Hui ; Chen, Lei ; Zhang, Yi-Quan ; Chen, Xue-Tai ; Wang, Zhenxing ; Ouyang, Zhong-Wen ; Yan, Hong ; Xue, Zi-Ling ( September 2021 , New Journal of Chemistry)

   Three mononuclear tetrakis(pseudohalido)-cobalt( ii ) complexes (Ph 4 P) 2 [Co(E) 4 ] (E = N 3 − , 1; NCO − , 2; NCS − , 3) have been synthesized and structurally characterized. Each compound contains a distorted tetrahedral Co 2+ ion coordinated by four pseudohalide ligands. The magnetic properties of 1–3 have been studied using direct-current magnetic measurements and high-frequency and -field EPR spectroscopy (HFEPR), suggesting easy-axis magnetic anisotropy for 1 and 2 and easy-plane anisotropy for 3. Analysis of the HFEPR spectra yielded D values of −5.23 and +3.63 cm −1 for 2 and 3, respectively. The absence of the EPR signal in 1 is consistent with a large, negative value of the zero-field splitting (ZFS) parameter D in 1. The nature of magnetic anisotropies of 1–3 has also been confirmed by ab initio calculations. The calculated D values are consistent with those determined using magnetometry and HFEPR studies. Alternating current (AC) magnetic susceptibilities reveal slow magnetic relaxation under an applied magnetic field, thus indicating that 1–3 are field-induced single-ion magnets (SIMs). 

   more » « less
3. Quantum electronic control on chemical activation of methane by collision with spin–orbit state selected vanadium cation

   https://doi.org/10.1039/D0CP04333H  

   Ng, Cheuk-Yiu ; Xu, Yuntao ; Chang, Yih-Chung ; Wannenmacher, Anna ; Parziale, Matthew ; Armentrout, P. B. ( January 2021 , Physical Chemistry Chemical Physics)

   null (Ed.)

   By coupling a newly developed quantum-electronic-state-selected supersonically cooled vanadium cation (V + ) beam source with a double quadrupole-double octopole (DQDO) ion–molecule reaction apparatus, we have investigated detailed absolute integral cross sections ( σ 's) for the reactions, V + [a 5 D J ( J = 0, 2), a 5 F J ( J = 1, 2), and a 3 F J ( J = 2, 3)] + CH 4 , covering the center-of-mass collision energy range of E cm = 0.1–10.0 eV. Three product channels, VH + + CH 3 , VCH 2 + + H 2 , and VCH 3 + + H, are unambiguously identified based on E cm -threshold measurements. No J -dependences for the σ curves ( σ versus E cm plots) of individual electronic states are discernible, which may indicate that the spin–orbit coupling is weak and has little effect on chemical reactivity. For all three product channels, the maximum σ values for the triplet a 3 F J state [ σ (a 3 F J )] are found to be more than ten times larger than those for the quintet σ (a 5 D J ) and σ (a 5 F J ) states, showing that a reaction mechanism favoring the conservation of total electron spin. Without performing a detailed theoretical study, we have tentatively interpreted that a weak quintet-to-triplet spin crossing is operative for the activation reaction. The σ (a 5 D 0 , a 5 F 1 , and a 3 F 2) measurements for the VH + , VCH 2 + , and VCH 3 + product ion channels along with accounting of the kinetic energy distribution due to the thermal broadening effect for CH 4 have allowed the determination of the 0 K bond dissociation energies: D 0 (V + –H) = 2.02 (0.05) eV, D 0 (V + –CH 2 ) = 3.40 (0.07) eV, and D 0 (V + –CH 3 ) = 2.07 (0.09) eV. Detailed branching ratios of product ion channels for the titled reaction have also been reported. Excellent simulations of the σ curves obtained previously for V + generated by surface ionization at 1800–2200 K can be achieved by the linear combination of the σ (a 5 D J , a 5 F J , and a 3 F J ) curves weighted by the corresponding Boltzmann populations of the electronic states. In addition to serving as a strong validation of the thermal equilibrium assumption for the populations of the V + electronic states in the hot filament ionization source, the agreement between these results also confirmed that the V + (a 5 D J , a 5 F J , and a 3 F J ) states prepared in this experiment are in single spin–orbit states with 100% purity. 

   more » « less
4. Monthly and Annual contour lines of the zero and the positive maximum of the Wind Stress Curl over Western North Atlantic during 1980-2019 and the Gulf Stream path during 1993-2019.

   https://doi.org/10.5281/zenodo.8217388  

   Gifford, Ian ; Silver, Adrienne ; Gangopadhyay, Avijit ; Andres, Magdalena ; Gawarkiewicz, Glen ; Oliver, Hilde ( January 2023 , Zenodo)

   This dataset includes multiple fields: (i) files for monthly and annual fields for the max curl line and the zero curl line at 0.1 degree longitudinal resolutions; (ii) files for monthly and annual GS path obtained from Altimetry and originally processed by Andres (2016) at 0.1 degree longitudinal resolution. The maximum curl line (MCL) and the zero curl line (ZCL) calculations are briefly described here and are based on the original wind data (at 1.25 x 1.25 degree) provided by the Japanese reanalysis (JRA-55; Kobayashi et al., 2015) and available at https://zenodo.org/record/8200832 (Gifford et al. 2023). For details see Gifford, 2023. 

   The wind stress curl (WSC) fields used for the MCL and ZCL calculations extend from 80W to 45W and 30N to 45N at the 1.25 by 1.25-degree resolution.  The MCL is defined as the maximum WSC values greater than zero within the domain per 1.25 degree longitude. As such, it is a function of longitude and is not a constant WSC value unlike the zero contour. High wind stress curl values that occurred near the coast were not included within this calculation. After MCL at the 1.25 resolution was obtained the line was smoothed with a gaussian smoothing and interpolated on to a 0.1 longitudinal resolution. The smoothed MCL lines at 0.1 degree resolution are provided in separate files for monthly and annual averages (2 files). Similarly, 2 other files (monthly and annual) are provided for the ZCL.    

   Like the MCL, the ZCL is a line derived from 1.25 degree longitude throughout the domain under the condition that it's the line of zero WSC. The ZCL is constant at 0 and does not vary spatially like the MCL. If there are more than one location of zero curl for a given longitude the first location south of the MCL is selected. Similar to the MCL, the ZCL was smoothed with a gaussian smoothing and interpolated on to a 0.1 longitudinal resolution.   

   The above files span the years from 1980 through 2019. So, the monthly files have 480 months starting January 1980, and the annual files have 40 years of data. The files are organized with each row being a new time step and each column being a different longitude. Therefore, the monthly MCL and ZCL files are each 480 x 351 for the 0.1 resolution data. Similarly, the annual files are 40 x 351 for the 0.1 degree resolution data.  

   Note that the monthly MCLs and ZCLs are obtained from the monthly wind-stress curl fields. The annual MCLs and ZCLs are obtained from the annual wind-stress curl fields.

   Since the monthly curl fields preserves more atmospheric mesoscales than the annual curl fields, the 12-month average of the monthly MCLs and ZCLs will not match with the annual MCLs and ZCLs derived from the annual curl field.  The annual MCLs and ZCLs provided here are obtained from the annual curl fields and representative metrics of the wind forcing on an annual time-scale. 

   Furthermore, the monthly Gulf Stream axis path (25 cm isoheight from Altimeter, reprocessed by Andres (2016) technique) from 1993 through 2019 have been made available here. A total of 324 monthly paths of the Gulf Stream are tabulated. In addition, the annual GS paths for these 27 years (1993-2019) of altimetry era have been put together for ease of use. The monthly Gulf Stream paths have been resampled and reprocessed for uniqueness at every 0.1 degree longitude from 75W to 50W and smoothed with a 100 km (10 point) running average via matlab. The uniqueness has been achieved by using Consolidator algorithm (D’Errico, 2023). 

   Each monthly or annual GS path has 251 points between 75W to 50W at 0.1 degree resolution.  

   Please contact igifford@earth.miami.edu for any queries. {"references": ["Andres, M., 2016. On the recent destabilization of the Gulf Stream path downstream of Cape Hatteras. Geophysical Research Letters, 43(18), 9836-9842.", "D'Errico, J., 2023. Consolidator (https://www.mathworks.com/matlabcentral/fileexchange/ 8354-consolidator), MATLAB Central File Exchange. Retrieved June 17, 2023.", "Gifford, Ian. H., 2023. The Synchronicity of the Gulf Stream Free Jet and the Wind Induced Cyclonic Vorticity Pool. MS Thesis, University of Massachusetts Dartmouth. 75pp.", "Gifford, Ian, H., Avijit Gangopadhyay, Magdalena Andres, Glen Gawarkiewicz, Hilde Oliver, Adrienne Silver, 2023. Wind Stress, Wind Stress Curl, and Upwelling Velocities in the Northwest Atlantic (80-45W, 30-45N) during 1980-2019, https://zenodo.org/record/8200832.", "Kobayashi, S., Ota, Y., Harada, Y., Ebita, A., Moriya, M., Onoda, H., Onogi, K., Kamahori, H., Kobayashi, C., Endo, H. and Miyaoka, K., 2015. The JRA-55 reanalysis: General specifications and basic characteristics.\u202fJournal of the Meteorological Society of Japan. Ser. II,\u202f93(1), pp.5-48. Kobayashi, S., Ota, Y., Harada, Y., Ebita, A., Moriya, M., Onoda, H., Onogi, K., Kamahori, H., Kobayashi, C., Endo, H. and Miyaoka, K., 2015. The JRA-55 reanalysis: General specifications and basic characteristics.\u202fJournal of the Meteorological Society of Japan. Ser. II,\u202f93(1), pp.5-48."]} 

   more » « less
5. Behavior of polyhedral built-up glass compression members

   Yost, Joseph Robert ; Akbarzadeh, Masoud ; Bolhassani, Mohammad ; Ryan, Liam ; Schneider, Jens ; Chhadeh, Philipp Amir ( July 2021 , International Conference on Civil Engineering and Architectural Design)

   null (Ed.)

   This research presents an experimental program executed to understand the strength and stiffness properties of hollow built-up glass compression members that are intended for use in the modular construction of all glass, compression-dominant, shell-type structures. The proposed compression-dominant geometric form has been developed using the methods of form finding and three-dimensional graphical statics. This research takes the first steps towards a new construction methodology for glass structures where individual hollow glass units (HGU) are assembled using an interlocking system to form large, compression-dominant, shell-type structures, thereby exploiting the high compression strength of glass. In this study, an individual HGU has an elongated hexagonal prism shape and consists of two deck plates, two long side plates, and four short side plates, as is shown in Figure 1. Connections between glass plates are made using a two-sided transparent structural adhesive tape. The test matrix includes four HGUs, two each fabricated with 1 mm and 2 mm thick adhesive tape. All samples are dimensioned 64 cm on the long axis of symmetry, 51 cm on the short axis of symmetry, and are 10 cm in width. Glass plates are all 10 mm thick annealed float glass with geometric fabrication done using 5-axis abrasive water jet cutting. HGU assembly is accomplished using 3D printed truing clips and results in a rigid three-dimensional glass frame. Testing was done with the HGU oriented such that load was introduced on the short side edges of the two deck plates, resulting in an asymmetric load-support condition. A soft interface material was used between the HGU and steel plates of the hydraulic actuator and support for the purpose of avoiding premature cracking from local stress concentrations on the glass edges at the load and support locations. Force was applied in displacement control at 0.25 mm/minute with a full array of displacement and strain sensors. Test results for load vs. center deck plate transverse deflection are shown in Figure 2. All samples failed explosively by flexural buckling with no premature cracking on the load and support edges of the deck plates. Strain and deformation data clearly show the presence of second-order behavior resulting from bending deformation perpendicular to the plane of the deck plates. In general, linear axial behavior transitions to nonlinear second-order behavior, with increasing rates in deflection and strain growth, ultimately ending in glass fracture on the tension surfaces of the buckled deck plates. The failure resulted in near-complete disintegration of the deck plates, but with no observable cracking in any side plates and a secure connection on all adhesive tape. Results of the experimental program clearly demonstrate the feasibility of using HGUs for modular construction of compression dominant all-glass shell-type structures. This method of construction can significantly reduce the self-weight of the structure, and it will inspire the use of sustainable materials in the construction of efficient structures. 

   more » « less