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1. Quadrupolar charge dynamics in the nonmagnetic FeSe 1−x S x superconductors

   https://doi.org/10.1073/pnas.2020585118  

   Zhang, Weilu ; Wu, Shangfei ; Kasahara, Shigeru ; Shibauchi, Takasada ; Matsuda, Yuji ; Blumberg, Girsh ( May 2021 , Proceedings of the National Academy of Sciences)

   null (Ed.)

   We use polarization-resolved electronic Raman spectroscopy to study quadrupolar charge dynamics in a nonmagnetic F e S e 1 − x S x superconductor. We observe two types of long-wavelength X Y symmetry excitations: 1) a low-energy quasi-elastic scattering peak (QEP) and 2) a broad electronic continuum with a maximum at 55 meV. Below the tetragonal-to-orthorhombic structural transition at T S ( x ) , a pseudogap suppression with temperature dependence reminiscent of the nematic order parameter develops in the X Y symmetry spectra of the electronic excitation continuum. The QEP exhibits critical enhancement upon cooling toward T S ( x ) . The intensity of the QEP grows with increasing sulfur concentration x and maximizes near critical concentration x c r ≈ 0.16 , while the pseudogap size decreases with the suppression of T S ( x ) . We interpret the development of the pseudogap in the quadrupole scattering channel as a manifestation of transition from the non-Fermi liquid regime, dominated by strong Pomeranchuk-like fluctuations giving rise to intense electronic continuum of excitations in the fourfold symmetric high-temperature phase, to the Fermi liquid regime in the broken-symmetry nematic phase where the quadrupole fluctuations are suppressed. 

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2. Alternative modes of bonding of C 4 F 8 units in mononuclear and binuclear iron carbonyl complexes

   https://doi.org/10.1039/C9NJ00882A  

   Huang, Liping ; Li, Jing ; Li, Guoliang ; Xie, Yaoming ; King, R. Bruce ; Schaefer, Henry F. ( May 2019 , New Journal of Chemistry)

   Density functional theory studies show that the lowest energy C 4 F 8 Fe(CO) 4 structure is not the very stable experimentally known ferracyclopentane isomer (CF 2 CF 2 CF 2 CF 2 )Fe(CO) 4 obtained from Fe(CO) 12 and tetrafluoroethylene. Instead isomeric (perfluoroolefin)Fe(CO) 4 structures derived from perfluoro-2-butene, perfluoro-1-butene, and perfluoro-2-methylpropene are significantly lower energy structures by up to ∼17 kcal mol −1 . However, the activation energies for the required fluorine shifts from one carbon to an adjacent carbon atom to form these (perfluoroolefin)Fe(CO) 4 complexes from tetrafluoroethylene are very high ( e.g. , ∼70 kcal mol −1 ). Therefore the ferracyclopentane isomer (CF 2 CF 2 CF 2 CF 2 )Fe(CO) 4 , which does not require a fluorine shift to form from Fe 3 (CO) 12 and tetrafluoroethylene, is the kinetically favored product. The lowest energy structures of the binuclear (C 4 F 8 ) 2 Fe 2 (CO) n ( n = 7, 6) derivatives have bridging perfluorocarbene ligands and terminal perfluoroolefin ligands. 

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3. Magnons and magnetic fluctuations in atomically thin MnBi2Te4

   https://doi.org/10.1038/s41467-022-29996-w  

   Lujan, David ; Choe, Jeongheon ; Rodriguez-Vega, Martin ; Ye, Zhipeng ; Leonardo, Aritz ; Nunley, T. Nathan ; Chang, Liang-Juan ; Lee, Shang-Fan ; Yan, Jiaqiang ; Fiete, Gregory A. ; et al ( December 2022 , Nature Communications)

   Abstract Electron band topology is combined with intrinsic magnetic orders in MnBi 2 Te 4 , leading to novel quantum phases. Here we investigate collective spin excitations (i.e. magnons) and spin fluctuations in atomically thin MnBi 2 Te 4 flakes using Raman spectroscopy. In a two-septuple layer with non-trivial topology, magnon characteristics evolve as an external magnetic field tunes the ground state through three ordered phases: antiferromagnet, canted antiferromagnet, and ferromagnet. The Raman selection rules are determined by both the crystal symmetry and magnetic order while the magnon energy is determined by different interaction terms. Using non-interacting spin-wave theory, we extract the spin-wave gap at zero magnetic field, an anisotropy energy, and interlayer exchange in bilayers. We also find magnetic fluctuations increase with reduced thickness, which may contribute to a less robust magnetic order in single layers. 

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4. Perfluoroolefin complexes versus perfluorometallacycles and perfluorocarbene complexes in cyclopentadienylcobalt chemistry

   https://doi.org/10.1039/C9CP06685C  

   Wen, Limei ; Li, Guoliang ; Xie, Yaoming ; King, R. Bruce ; Schaefer, Henry F. ( April 2020 , Physical Chemistry Chemical Physics)

   Fluorocarbons have been shown experimentally by Baker and coworkers to combine with the cyclopentadienylcobalt (CpCo) moiety to form fluoroolefin and fluorocarbene complexes as well as fluorinated cobaltacyclic rings. In this connection density functional theory (DFT) studies on the cyclopentadienylcobalt fluorocarbon complexes CpCo(L)(C n F 2n ) (L = CO, PMe 3 ; n = 3 and 4) indicate structures with perfluoroolefin ligands to be the lowest energy structures followed by perfluorometallacycle structures and finally by structures with perfluorocarbene ligands. Thus, for the CpCo(L)(C 3 F 6 ) (L = CO, PMe 3 ) complexes, the perfluoropropene structure has the lowest energy, followed by the perfluorocobaltacyclobutane structure and the perfluoroisopropylidene structure less stable by 8 to 11 kcal mol −1 , and the highest energy perfluoropropylidene structure less stable by more than 12 kcal mol −1 . For the two metal carbene structures Cp(L)CoC(CF 3 ) 2 and Cp(L)CoCF(C 2 F 5 ), the former is more stable than the latter, even though the latter has Fischer carbene character. For the CpCo(L)(C 4 F 8 ) (L = CO, PMe 3 ) complexes, the perfluoroolefin complex structures have the lowest energies, followed by the perfluorometallacycle structures at 10 to 20 kcal mol −1 , and the structures with perfluorocarbene ligands at yet higher energies more than 20 kcal mol −1 above the lowest energy structure. This is consistent with the experimentally observed isomerization of the perfluorinated cobaltacyclobutane complexes CpCo(PPh 2 Me)(–CFR–CF 2 –CF 2 –) (R = F, CF 3 ) to the perfluoroolefin complexes CpCo(PPh 2 Me)(RCFCF 2 ) in the presence of catalytic quantities of HN(SO 2 CF 3 ) 2 . Further refinement of the relative energies by the state-of-the-art DLPNO-CCSD(T) method gives results essentially consistent with the DFT results summarized above. 

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5. Quadrupolar magnetic excitations in an isotropic spin-1 antiferromagnet

   https://doi.org/10.1038/s41467-022-30065-5  

   Nag, A. ; Nocera, A. ; Agrestini, S. ; Garcia-Fernandez, M. ; Walters, A. C. ; Cheong, Sang-Wook ; Johnston, S. ; Zhou, Ke-Jin ( December 2022 , Nature Communications)

   Abstract The microscopic origins of emergent behaviours in condensed matter systems are encoded in their excitations. In ordinary magnetic materials, single spin-flips give rise to collective dipolar magnetic excitations called magnons. Likewise, multiple spin-flips can give rise to multipolar magnetic excitations in magnetic materials with spin S ≥ 1. Unfortunately, since most experimental probes are governed by dipolar selection rules, collective multipolar excitations have generally remained elusive. For instance, only dipolar magnetic excitations have been observed in isotropic S = 1 Haldane spin systems. Here, we unveil a hidden quadrupolar constituent of the spin dynamics in antiferromagnetic S = 1 Haldane chain material Y 2 BaNiO 5 using Ni L 3 -edge resonant inelastic x-ray scattering. Our results demonstrate that pure quadrupolar magnetic excitations can be probed without direct interactions with dipolar excitations or anisotropic perturbations. Originating from on-site double spin-flip processes, the quadrupolar magnetic excitations in Y 2 BaNiO 5 show a remarkable dual nature of collective dispersion. While one component propagates as non-interacting entities, the other behaves as a bound quadrupolar magnetic wave. This result highlights the rich and largely unexplored physics of higher-order magnetic excitations. 

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