Red shift in the absorption spectrum of phototropin LOV1 upon the formation of a semiquinone radical: reconstructing the orbital architecture

Flavin mononucleotide (FMN) is a ubiquitous blue-light pigment due to its ability to drive one- and two-electron transfer reactions. In both light-oxygen-voltage (LOV) domains of phototropin from the green algae Chlamydomonas reinhardtii, FMN is noncovalently bound. In the LOV1 cysteine-to-serine mutant (C57S), light-induced electron transfer from a nearby tryptophan occurs, and a transient spin-correlated radical pair (SCRP) is formed. Within this photocycle, nuclear hyperpolarization is created by the solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) effect. In a side reaction, a stable protonated semiquinone radical (FMNH·) forms undergoing a significant bathochromic shift of the first electronic transition from 445 to 591 nm. The incorporation of phototropin LOV1-C57S into an amorphous trehalose matrix, stabilizing the radical, allows for application of various magnetic resonance experiments at ambient temperatures, which are combined with quantum-chemical calculations. As a result, the bathochromic shift of the first absorption band is explained by lifting the degeneracy of the molecular orbital energy levels for electrons with alpha and beta spins in FMNH· due to the additional electron

Spin resonance linewidths of bismuth donors in silicon coupled to planar microresonators

Ensembles of bismuth donor spins in silicon are promising storage elements for microwave quantum memories due to their long coherence times which exceed seconds. Operating an efficient quantum memory requires achieving critical coupling between the spin ensemble and a suitable high-quality factor resonator -- this in turn requires a thorough understanding of the lineshapes for the relevant spin resonance transitions, particularly considering the influence of the resonator itself on line broadening. Here, we present pulsed electron spin resonance measurements of ensembles of bismuth donors in natural silicon, above which niobium superconducting resonators have been patterned. By studying spin transitions across a range of frequencies and fields we identify distinct line broadening mechanisms, and in particular those which can be suppressed by operating at magnetic-field-insensitive `clock transitions'. Given the donor concentrations and resonator used here, we measure a cooperativity $C\sim 0.2$ and based on our findings we discuss a route to achieve unit cooperativity, as required for a quantum memory

Random-access quantum memory using chirped pulse phase encoding

Quantum memories capable of faithfully storing and recalling quantum states on-demand are powerful ingredients in bulding quantum networks [arXiv:0806.4195] and quantum information processors [arXiv:1109.3743]. As in conventional computing, key attributes of such memories are high storage density and, crucially, random access, or the ability to read from or write to an arbitrarily chosen register. However, achieving such random access with quantum memories [arXiv:1904.09643] in a dense, hardware-efficient manner remains a challenge, for example requiring dedicated cavities per qubit [arXiv:1109.3743] or pulsed field gradients [arXiv:0908.0101]. Here we introduce a protocol using chirped pulses to encode qubits within an ensemble of quantum two-level systems, offering both random access and naturally supporting dynamical decoupling to enhance the memory lifetime. We demonstrate the protocol in the microwave regime using donor spins in silicon coupled to a superconducting cavity, storing up to four multi-photon microwave pulses and retrieving them on-demand up to 2~ms later. A further advantage is the natural suppression of superradiant echo emission, which we show is critical when approaching unit cooperativity. This approach offers the potential for microwave random access quantum memories with lifetimes exceeding seconds [arXiv:1301.6567, arXiv:2005.09275], while the chirped pulse phase encoding could also be applied in the optical regime to enhance quantum repeaters and networks

Coherent spin dynamics of rare-earth doped crystals in the high-cooperativity regime

Rare-earth doped crystals have long coherence times and the potential to provide quantum interfaces between microwave and optical photons. Such applications benefit from a high cooperativity between the spin ensemble and a microwave cavity -- this motivates an increase in the rare earth ion concentration which in turn impacts the spin coherence lifetime. We measure spin dynamics of two rare-earth spin species, $^{145}$Nd and Yb doped into Y$_{2}$SiO$_{5}$, coupled to a planar microwave resonator in the high cooperativity regime, in the temperature range 1.2 K to 14 mK. We identify relevant decoherence mechanisms including instantaneous diffusion arising from resonant spins and temperature-dependent spectral diffusion from impurity electron and nuclear spins in the environment. We explore two methods to mitigate the effects of spectral diffusion in the Yb system in the low-temperature limit, first, using magnetic fields of up to 1 T to suppress impurity spin dynamics and, second, using transitions with low effective g-factors to reduce sensitivity to such dynamics. Finally, we demonstrate how the `clock transition' present in the $^{171}$Yb system at zero field can be used to increase coherence times up to $T_{2} = 6(1)$ ms.Comment: 8 pages, 5 figure

Hibridinių metalo-formiato karkasų tyrimai elektronų paramagnetinio rezonanso spektroskopija

The dissertation is dedicated to electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) study of structural phase transitions, structural phases and dynamic effects in hybrid metal-formate frameworks. The continuous-wave EPR experiments allowed to characterize the order of the structural phase transitions and motion of the molecular cations in the disordered phases of [(CH3)2NH2][Zn(HCOO)3], [CH3NH2NH2][Zn(HCOO)3] and [NH3(CH2)4NH3][Zn(HCOO)3]2 hybrid frameworks. EPR measurements with an external electric field revealed non-ferroelectric nature of the dimethylammonium zinc-formate, while [NH4][Zn(HCOO)3] framework proved to be ferroelectric. The pulsed EPR spectroscopy allowed to probe the motion of the methyl groups in the ordered phases as well as the lattice dynamics in the vicinity of the structural phase transitions in zinc-formate frameworks. The pulsed ENDOR experiments verified the proton positions in the structural models of these compounds

Electron paramagnetic resonance spectroscopy of hybrid metal-formate frameworks

The dissertation is dedicated to electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) study of structural phase transitions, structural phases and dynamic effects in hybrid metal-formate frameworks. The continuous-wave EPR experiments allowed to characterize the order of the structural phase transitions and motion of the molecular cations in the disordered phases of [(CH3)2NH2][Zn(HCOO)3], [CH3NH2NH2][Zn(HCOO)3] and [NH3(CH2)4NH3][Zn(HCOO)3]2 hybrid frameworks. EPR measurements with an external electric field revealed non-ferroelectric nature of the dimethylammonium zinc-formate, while [NH4][Zn(HCOO)3] framework proved to be ferroelectric. The pulsed EPR spectroscopy allowed to probe the motion of the methyl groups in the ordered phases as well as the lattice dynamics in the vicinity of the structural phase transitions in zinc-formate frameworks. The pulsed ENDOR experiments verified the proton positions in the structural models of these compounds

Phase transitions and dynamics in mixed three- and low-dimensional lead halide perovskites /

Lead halide perovskites are extensively investigated as efficient solution-processable materials for photovoltaic applications. The greatest stability and performance of these compounds are achieved by mixing different ions at all three sites of the APbX3 structure. Despite the extensive use of mixed lead halide perovskites in photovoltaic devices, a detailed and systematic understanding of the mixing-induced effects on the structural and dynamic aspects of these materials is still lacking. The goal of this review is to summarize the current state of knowledge on mixing effects on the structural phase transitions, crystal symmetry, cation and lattice dynamics, and phase diagrams of three- and low-dimensional lead halide perovskites. This review analyzes different mixing recipes and ingredients providing a comprehensive picture of mixing effects and their relation to the attractive properties of these materials

Effect of sintering under CO+N2/H2 and CO2+air atmospheres on the physicochemical features of a commercial nano-YSZ /

Given the need to process anodes and composites based on nano-YSZ in reducing or in air containing additional CO2 atmospheres for the fabrication of solid oxide fuel cells (SOFCs), and solid oxide electrolysis cells (SOECs), we have studied the effect of the exposure to CO+N2/H2 or CO2+air mixtures during sintering of YSZ green pellets, prepared from commercial nanopowders, on their structure, microstructure, chemical composition and their electrical properties. The reduced sample shows Raman bands at 1298 and 1605 cm−1 that are assigned to the D and G bands of carbon, respectively. The bands intensity ratio ID/IG indicates a larger content of disordered carbon. X-ray photoelectron spectroscopy (XPS) shows that C is present in the reduced samples as reduced carbon. However, the samples sintered in CO2+air present C as carbonate-type. Impedance spectroscopy reveals that the highest total conductivity is for the reduced samples in the whole range of studied temperatures. In addition, sintering in CO2+air causes a detrimental effect on the grain boundary conductivity and therefore, on the total electrical conductivity of YSZ. It can be due to the pre sence of impurities such as carbonates and oxidised or even, polymerised carbonaceous species located at those areas