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Gopalan Rajaraman

Publications and source records attributed to Gopalan Rajaraman.

4 recordsLinked to original sources

Hexagonal Boron Nitride Spin Defects for Quantum Photonics: Annealing-Free Generation by Krypton Ion Implantation

Controlled, reproducible generation of luminescent defect centres in hBN remains a key challenge for scalable quantum-photonic technologies. Here, we report Kr$^{+}$ ion implantation as a tunable, annealing-free, and chemically inert route to room-temperature near-infrared luminescent spin defects in hBN, requiring no pre- or post-implantation annealing. SRIM Monte Carlo simulations were used to optimise the parameters for 40 keV Kr$^{+}$ irradiation of hBN flakes. The implanted samples exhibit a stable near-infrared photoluminescence (PL) band centred at $\sim$830 nm whose intensity increases with implantation fluence over $10^{11}$-$10^{15}$ions/cm$^{2}$. Temperature-dependent PL measurements (20-300 K) reveal a linewidth broadening well described by a $T^{3}$ dependence, consistent with acoustic-phonon-mediated dephasing. Raman spectra show the characteristic $E_{2g}$ mode of pristine hBN at $\sim$1366 cm$^{-1}$ alongside an implantation-induced defect feature at $\sim$1295 cm$^{-1}$, confirming irradiation-induced lattice disorder. Electron paramagnetic resonance (EPR) measurements reveal a paramagnetic centre with a $g$-factor of 2.003, and density functional theory (DFT) calculations indicate that a spatially separated $V_{\mathrm{N}}$-$C_{\mathrm{B}}$ donor-acceptor pair complex is a viable origin of the observed optical and magnetic signatures. Overall, Kr$^{+}$ implantation offers an effective, annealing-free, and scalable platform for generating stable room-temperature luminescent defects, providing a promising route toward quantum photonics.

physics.optics

Atomic-scale visualization of the toroidal order in a trimeric Dy(III) single-molecule toroic

Single-molecule toroics (SMTs) offer a unique platform for next-generation quantum devices utilizing head-to-tail spin alignments in the compounds. Presence of toroidal moments in SMTs has been essentially based on magnetometry and ab initio calculations. Here, we report observation and probe of the toroidal moment in [Dy3(OH)(teaH2)3(paa)3]Cl(OMe) [teaH3: triethanolamine; paaH: N-(2-pyridyl)-acetoacetamide] from mapping of Dy3+ magnetic susceptibility tensors by polarized neutron diffraction (PND). Neutron diffraction under variable magnetic fields demonstrates field-induced magnetization along the c-axis with toroidal moments anti-parallelly stacked, providing definite proof of the toroidal moment. Magnetometry studies confirm the toroidal ground state. For the first time, the combined use of PND, variable-field neutron diffraction, ab initio calculations, and magnetometry is introduced as a robust and quantitative methodology to probe molecular-scale toroidal magnetism. This integrated approach overcomes limitations of earlier indirect methods, establishes a benchmark framework for investigating SMTs, and provides valuable insights for the design of molecular quantum materials.

cond-mat.str-el

The Mechanism of Spin-Phonon Relaxation in Endohedral Metallofullene Single Molecule Magnets

This study presents the first-ever investigation of spin-phonon coupling mechanisms in fullerene-based single-molecule magnets (SMMs) using ab initio CASSCF combined with DFT calculations. While lanthanide-based SMMs, particularly those with DyIII ions, are known for their impressive blocking temperatures and relaxation barriers, endohedral metallofullerene (EMFs) offer a unique platform for housing low-coordinated lanthanides within rigid carbon cages. We have explored the spin dynamics of in DyScS@C82 exhibiting among the highest blocking temperature (TB) reported. Through our computational analysis, we reveal that while the fullerene cage enhances crystal field splitting and provides structural stability without significantly contributing to spin-relaxation-driving low-energy phonons, the internal ionic motion emerges as the primary factor controlling spin relaxation and limiting blocking temperature. This computational investigation into the spin dynamics of EMF-based SMMs provides key insights into their magnetic behaviour for the first time an

cond-mat.mtrl-sci

Ferrotoroidic Ground State in a Heterometallic Cr$^{\mathrm{III}}$Dy$^{\mathrm{III}}_6$ Complex Displaying Slow Magnetic Relaxation

Toroidal quantum states are most promising for building quantum computing and information storage devices as they are insensitive to homogeneous magnetic fields, but interact with charge and spin currents, allowing this moment to be manipulated purely by electrical means. Coupling molecular toroids into larger toroidal moments via ferrotoroidic interactions can be pivotal not only to enhance ground state toroidicity, but also to develop materials displaying ferrotoroidic ordered phases, which sustain linear magneto-electric coupling and multiferroic behaviour. However, engineering ferrotoroidic coupling is known to be a challenging task. Here we have isolated a Cr$^{\mathrm{III}}$Dy$^{\mathrm{III}}_6$ complex, which exhibits the much sought-after ferrotoroidic ground state with an enhanced toroidal moment, solely arising from intramolecular dipolar interactions. Moreover, a theoretical analysis of the observed sub-Kelvin zero-field hysteretic spin dynamics of Cr$^{\mathrm{III}}$Dy$^{\mathrm{III}}_6$ reveals the pivotal role played by ferrotoroidic states in slowing down the magnetic relaxation, in spite of large calculated single-ion quantum tunnelling rates.

physics.chem-ph