arXiv subjects

Sam L. Bayliss

Publications and source records attributed to Sam L. Bayliss.

8 recordsLinked to original sources

arXiv2026

Understanding the spin coherence of molecular photoexcited triplet states from first principles

Optically readable molecular spins are attractive as quantum sensors due to their nanoscale modularity, synthetic tunability, and scope for sensitive readout. In particular, photoexcited spin-triplet states in organic molecules are appealing in supporting high optical-spin contrast at room temperature. Their utility is underpinned by their coherence, which warrants a detailed understanding of it. Here, from first principles, we systematically explore the Hahn-echo decoherence of the benchmark molecular system for room-temperature optically detected spin coherence---pentacene guest molecules coupled to a para-terphenyl host. Using generalized cluster-correlation expansion methods, we investigate the mechanisms of nuclear-spin-induced decoherence from zero to high magnetic field, exploring the role of guest vs host molecules, specific nuclei, zero-field splitting interactions, and hyperfine parameters. We describe how zero-field decoherence is driven by ~6 nuclei on the guest, while high-field decoherence is driven by ~600 nuclei in the host; how the longitudinal zero-field splitting parameter, $D$, can prolong $T_2$; and the magnetic-field-dependent processes which drive decoherence. These results advance our understanding of decoherence in optically readable molecular spins, providing insight for their synthetic enhancement and deployment as quantum probes.

quant-ph↗

arXiv2026

Host-guest Crystal Engineering Tailors the Room Temperature Spin Dynamics in Molecular Quantum Devices

Molecular materials that enable coherent control over an electron's spin state at room temperature are promising candidates for quantum technologies, including quantum sensors and ultra-low noise microwave amplifiers, known as masers. Host-guest molecular crystals enable independent control of spin-active guests and their local environments to enhance molecular spin properties and so improve device performance. Using electron paramagnetic resonance and optically-detected magnetic resonance, we demonstrate the ability to tune triplet population, depopulation, and spin-lattice relaxation by modulating host-dependent lattice rigidity and vibrational coupling to significantly reduce the operating requirements for building useful masers. Importantly, the most rigid host, picene, reveals the ability to slow spin-lattice relaxation without lengthening triplet lifetime, though at the cost of strain-induced line width broadening and reduced triplet spin polarisation. We also find that deuteration reduces the triplet resonance line width and vibrationally-mediated triplet depopulation. Consequently, we find that perdeuterated pentacene in perdeuterated p-terphenyl is the most viable candidate for building a continuous wave maser. This work demonstrates host-guest engineering as an important and practical method for tuning the spin-dependent performance of room-temperature molecular quantum technologies.

quant-ph↗

arXiv2025

Room temperature optical control of spin states in organic diradicals

We report a family of luminescent alternant diradicals which, at room temperature, support a ground-state spin-triplet, near-unity photoluminescence quantum yields, and optical spin addressability. These diradicals comprise trityl groups meta-linked via pyridyl or phenyl groups, enabling optically bright triplet-to-triplet and singlet-to-singlet transitions. At room temperature, we observe optically detected magnetic resonance in these systems at zero magnetic field and a strong magneto-photoluminescence (10% modulation at 2 mT applied magnetic field). Distinct photoluminescence bands (at 630 nm and 700 nm) show opposite-sign spin-optical responses, arising from spin-selective intersystem crossing between triplet and singlet manifolds. These bright, all-organic diradicals offer a new set of chemically tunable materials for room temperature spin-optical interfaces, paving the way for application as quantum sensors.

cond-mat.mtrl-sci↗

arXiv2025

Chemically Tuning Room Temperature Pulsed Optically Detected Magnetic Resonance

Optical detection of magnetic resonance enables spin-based quantum sensing with high spatial resolution and sensitivity-even at room temperature-as exemplified by solid-state defects. Molecular systems provide a complementary, chemically tunable, platform for room-temperature optically detected magnetic resonance (ODMR)-based quantum sensing. A critical parameter governing sensing sensitivity is the optical contrast-i.e., the difference in emission between two spin states. In state-of-the-art solid-state defects such as the nitrogen-vacancy center in diamond, this contrast is approximately 30%. Here, capitalizing on chemical tunability, we show that room-temperature ODMR contrasts of 40% can be achieved in molecules. Using a nitrogen-substituted analogue of pentacene (6,13-diazapentacene), we enhance contrast compared to pentacene and, by determining the triplet kinetics through time-dependent pulsed ODMR, show how this arises from accelerated anisotropic intersystem crossing. Furthermore, we translate high-contrast room-temperature pulsed ODMR to self-assembled nanocrystals. Overall, our findings highlight the synthetic handles available to optically readable molecular spins and the opportunities to capitalize on chemical tunability for room-temperature quantum sensing.

quant-ph↗

arXiv2024

Room-temperature optically detected coherent control of molecular spins

Benefiting from both molecular tunability and versatile methods for deployment, optically interfaced molecular spins are a promising platform for quantum technologies such as sensing and imaging. Room-temperature optically detected coherent spin control is a key enabler for many applications, combining sensitive readout, versatile spin manipulation, and ambient operation. Here we demonstrate such functionality in a molecular spin system. Using the photoexcited triplet state of organic chromophores (pentacene doped in a para-terphenyl host), we optically detect coherent spin manipulation with photoluminescence contrasts exceeding 10% and microsecond coherence times at room temperature. We further demonstrate how coherent control of multiple triplet sublevels can significantly enhance optical spin contrast, and extend optically detected coherent control to a thermally evaporated thin film, retaining high photoluminescence contrast and coherence times of order one microsecond. These results open opportunities for room-temperature quantum technologies that can be systematically tailored through synthetic chemistry.

quant-ph↗

arXiv2019

Electrically driven optical interferometry with spins in silicon carbide

Interfacing solid-state defect electron spins to other quantum systems is an ongoing challenge. The ground-state spin's weak coupling to its environment bestows excellent coherence properties, but also limits desired drive fields. The excited-state orbitals of these electrons, however, can exhibit stronger coupling to phononic and electric fields. Here, we demonstrate electrically driven coherent quantum interference in the optical transition of single, basally oriented divacancies in commercially available 4H silicon carbide. By applying microwave frequency electric fields, we coherently drive the divacancy's excited-state orbitals and induce Landau-Zener-Stuckelberg interference fringes in the resonant optical absorption spectrum. Additionally, we find remarkably coherent optical and spin subsystems enabled by the basal divacancy's symmetry. These properties establish divacancies as strong candidates for quantum communication and hybrid system applications, where simultaneous control over optical and spin degrees of freedom is paramount.

quant-ph↗

arXiv2018

Site-selective measurement of coupled spin pairs in an organic semiconductor

From organic electronics to biological systems, understanding the role of intermolecular interactions between spin pairs is a key challenge. Here we show how such pairs can be selectively addressed with combined spin and optical sensitivity. We demonstrate this for bound pairs of spin-triplet excitations formed by singlet fission, with direct applicability across a wide range of synthetic and biological systems. We show that the site-sensitivity of exchange coupling allows distinct triplet pairs to be resonantly addressed at different magnetic fields, tuning them between optically bright singlet (S=0) and dark triplet, quintet (S=1,2) configurations: this induces narrow holes in a broad optical emission spectrum, uncovering exchange-specific luminescence. Using fields up to 60 T, we identify three distinct triplet-pair sites, with exchange couplings varying over an order of magnitude (0.3-5 meV), each with its own luminescence spectrum, coexisting in a single material. Our results reveal how site-selectivity can be achieved for organic spin pairs in a broad range of systems.

physics.chem-ph↗

arXiv2017

Ultrafast Triplet Pair Formation and Subsequent Thermally Activated Dissociation Control Efficient Endothermic Singlet Exciton Fission

Singlet exciton fission (SF), the conversion of one spin-singlet exciton (S1) into two spin-triplet excitons (T1), could provide a means to overcome the Shockley-Queisser limit in photovoltaics. SF as measured by the decay of S1 has been shown to occur efficiently and independently of temperature even when the energy of S1 is as much as 200 meV less than 2T1. Here, we study films of TIPS-tetracene using transient optical spectroscopy and show that the initial rise of the triplet pair state (TT) occurs in 300 fs, matched by rapid loss of S1 stimulated emission, and that this process is mediated by the strong coupling of electronic and vibrational degrees of freedom. This is followed by a slower 10 ps morphology-dependent phase of S1 decay and TT growth. We observe the TT to be thermally dissociated on 10-100 ns timescales to form free triplets. This provides a model for "temperature independent", efficient TT formation and thermally activated TT separation.

physics.chem-ph↗