Two B-site ordered double perovskites, La 2 LiReO 6 and Ba 2 YReO 6 , with S = 1 were investigated as geometrically frustrated antiferromagnets, using x-ray and neutron diffraction, superconducting quantum interference device magnetometry, heat capacity, muon spin relaxation ͑SR͒, and 89 Y magic-angle spinning ͑MAS͒ NMR. La 2 LiReO 6 has a monoclinic structure ͑P2 1 / n͒ with cell parameters at room temperature; a = 5.58262͑22͒ Å, b = 5.67582͑20͒ Å, c = 7.88586͑27͒ Å, and ␤ = 90.240͑4͒°. A zero-field cooled/field cooled ͑ZFC/FC͒ divergence at 50 K was observed in the susceptibility. The ZFC susceptibility is zero below ϳ5 K for polycrystalline samples, suggesting a cooperative singlet ground state but weak moments are induced by cooling in very small fields ϳ1 mT. No evidence of long-range ordering is evident in heat capacity, neutrondiffraction, or SR data. The ZF spin dynamics from SR are anomalous and can be fitted to a stretched exponential rather than the Kubo-Toyabe form expected for random frozen spins but the muon spins are decoupled in longitudinal fields ͑LF͒, consistent with spin freezing of the fraction of spins relaxing within the muon time scale. The internal fields sensed by the muons are anomalously small, consistent with an electronic spin-singlet state. Ba 2 YReO 6 is found to be cubic ͑Fm3m͒ with cell parameter a = 8.36278͑2͒ Å at 300 K with no change in symmetry at 3.8 K, at variance with the Jahn-Teller theorem for a t 2g 2 configuration for Re 5+ . 89 Y MAS NMR shows a single peak indicating that Y/Re site disorder is at most 0.5%. The susceptibility shows two broad peaks around 50 and 25 K but no evidence for long-range order from heat capacity, neutron diffraction, or SR. The ZF SR result shows a two-component ground state with both slow and fast relaxations and decoupling results in a 1 kG LF, indicating spin freezing. These results are in sharp contrast to the long-range AF order found in the S =3/ 2 isostructural materials, La 2 LiRuO 6 and Ba 2 YRuO 6 , indicating that the reduction to S = 1 plays a major role in ground state determination.

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The B-site ordered double perovskite Ba2CaOsO6 was studied by dc magnetic susceptibility, powder neutron diffraction and muon spin relaxation methods. The lattice parameter is a = 8.3619(6) Å at 280 K and cubic symmetry [Formula: see text] is retained to 3.5 K with a = 8.3462(7) Å. Curie-Weiss susceptibility behaviour is observed for T > 100 K and the derived constants are C = 0.3361(3) emu K mol(-1) and ΘCW = -156.2(3) K, in excellent agreement with literature values. This Curie constant is much smaller than the spin-only value of 1.00 emu K mol(-1) for a 5d(2) Os(6+) configuration, indicating a major influence of spin-orbit coupling. Previous studies had detected both susceptibility and heat capacity anomalies near 50 K but no definitive conclusion was drawn concerning the nature of the ground state. While no ordered Os moment could be detected by powder neutron diffraction, muon spin relaxation (µSR) data show clear long-lived oscillations indicative of a continuous transition to long-range magnetic order below TC = 50 K. An estimate of the ordered moment on Os(6+) is ∼ 0.2 μB, based upon a comparison with µSR data for Ba2YRuO6 with a known ordered moment of 2.2 μB. These results are compared with those for isostructural Ba2YReO6 which contains Re(5+), also 5d(2), and has a nearly identical unit cell constant, a = 8.36278(2) Å-a structural doppelgänger. In contrast, Ba2YReO6 shows ΘCW = - 616 K, and a complex spin-disordered and, ultimately, spin-frozen ground state below 50 K, indicating a much higher level of geometric frustration than in Ba2CaOsO6. The results on these 5d(2) systems are compared to recent theory, which predicts a variety of ferromagnetic and antiferromagnetic ground states. In the case of Ba2CaOsO6, our data indicate that a complex four-sublattice magnetic structure is likely. This is in contrast to the spin-disordered ground state in Ba2YReO6, despite a lack of evidence for structural disorder, for which theory currently provides no clear explanation.

Two B-site ordered double perovskites, La 2 LiMoO 6 and Ba 2 YMoO 6 , based on the S = PHYSICAL REVIEW B 81, 224409 ͑2010͒

Triplet and in-gap magnetic states in the ground state of the quantum frustrated fcc antiferromagnet Ba2YMoO6 Carlo, J. P.; Clancy, J. P.; Aharen, T.; Yamani, Z.; Ruff, J. P. C.; Wagman, J. J.; Van Gastel, G The geometrically frustrated double perovskite Ba 2 YMoO 6 is characterized by quantum s = 1/2 spins at the Mo 5+ sites of an undistorted fcc lattice. Previous low-temperature characterization revealed an absence of static long-range magnetic order and suggested a nonmagnetic spin-singlet ground state. We report unique time-of-flight and triple-axis neutron spectroscopy of Ba 2 YMoO 6 that shows a 28 meV spin excitation with a bandwidth of ∼4 meV, which vanishes above ∼125 K. We identify this as the singlet-triplet excitation that arises out of a singlet ground state, and further identify a weaker continuum of magnetic states within the gap, reminiscent of spin-polaron states arising due to weak disorder.

The water dimer is an ideal chemical species with which to study hydrogen bonds. Owing to the equilibrium between the monomer and oligomer structure, however, selective generation and separation of a genuine water dimer has not yet been achieved. Here, we report a synthetic strategy that leads to the successful encapsulation of one or two water molecules inside fullerene C70. These endohedral C70 compounds offer the opportunity to study the intrinsic properties of a single water molecule without any hydrogen bonding, as well as an isolated water dimer with a single hydrogen bond between the two molecules. The unambiguously determined off-centre position of water in (H2O)2@C70 by X-ray diffraction provides insights into the formation of (H2O)2@C70. Subsequently, the (1)H NMR spectroscopic measurements for (H2O)2@C70 confirmed the formation of a single hydrogen bond rapidly interchanging between the encapsulated water dimer. Our theoretical calculations revealed a peculiar cis-linear conformation of the dimer resulting from confinement effects inside C70.

We performed terahertz time-domain spectroscopy for methylammonium (MA) lead halide perovskite single crystals and characterized the longitudinal optical (LO) phonons directly. We found that the effective LO phonon wave number does not change in the wide temperature range between 10 and 300 K. However, the coupling between MA cation modes and the LO phonon mode derived from lead halide cages induces a mode splitting at low temperatures and a damping of the LO phonon mode at high temperatures. These results influence the interpretation of electron-LO phonon interactions in perovskite semiconductors, as well as the interpretations of mobility, carrier diffusion, and polaron formation.

Lead halide perovskite nanocrystals are promising light emitting materials with high photoluminescence quantum yields and widely tunable emission wavelengths. Their optical responses are significantly influenced by efficient nonradiative Auger recombination of trions (charged excitons) and biexcitons. Here, we report the observation of positive and negative trions in formamidinium lead bromide nanocrystals and discuss their role in the photoluminescence dynamics. It is found that the addition of copper thiocyanate causes an additional intermediate state by photochemical doping. We clarify that as-prepared nanocrystals show a two-state blinking between neutral excitons and positive trions, while the postsynthesis treated nanocrystals exhibit blinking between all three states, including negative trions. We confirmed that the biexciton Auger rate evaluated from femtosecond transient absorption measurements can be expressed as the sum of the Auger rates of positive and negative trions obtained by single-dot spectroscopy.