arXiv subjects

Jenny Clark

Publications and source records attributed to Jenny Clark.

8 recordsLinked to original sources

arXiv2024

Singlet fission contributes to solar energy harvesting in photosynthesis

Singlet fission (SF), the spin-allowed conversion of one singlet exciton into two triplet excitons, offers a promising strategy for enhancing the efficiency of photovoltaic devices. However, realising this potential necessitates materials capable of ultrafast (sub-picosecond) SF and the generation of long-lived (> microsecond) triplet excitons, a synthetic challenge. Some photosynthetic organisms have evolved sophisticated molecular architectures that demonstrate these criteria, but despite 40 years of study, the underlying SF mechanisms and its functional significance in these organisms remain unclear. Here, we use a suite of ultrafast and magneto-optical spectroscopic techniques to understand the mechanism of SF within light-harvesting 1 (LH1) complexes from wild-type and genetically modified photosynthetic bacteria. Our findings reveal a SF process, termed "heterofission", wherein singlet excitons are transformed into triplet excitons localised on adjacent carotenoid (Crt) and bacteriochlorophyll (BChl) molecules. We also uncover an unexpected functional role for SF in augmenting Crt-to-BChl photosynthetic energy transfer efficiency. By transiently storing electronic excitation within the SF-generated triplet pair, the system circumvents rapid thermalisation of Crt excitations, thereby enhancing energy transfer efficiency to the BChl Qy state, and enabling the organism to usefully harvest more sunlight.

physics.bio-ph↗

arXiv2024

High-Spin State Dynamics and Quintet-Mediated Emission in Intramolecular Singlet Fission

High-spin states in molecular systems hold significant interest for a wide range of applications ranging from optoelectronics to quantum information and singlet fission (SF). Quintet and triplet states play crucial roles, particularly in SF systems, necessitating a precise monitoring and control of their spin dynamics. Spin states in intramolecular SF (iSF) are of particular interest, but tuning these systems to control triplet multiplication pathways has not been extensively studied. Additionally, whilst studies in this context focus on participation of triplet pathways leading to photoluminescence, emission pathways via quintet states remain largely unexplored. Here, we employ a set of unique spin-sensitive techniques to investigate high-spin state formation and emission in dimers and trimers comprising multiple diphenylhexatriene (DPH) units. We demonstrate the formation of pure quintet states in all these oligomers, with high-spin state optical emission via quintet states dominating delayed fluorescence up to room temperature. For triplet formation, we distinguish between the ability to form weakly exchange-coupled triplet pairs and the efficiency-reducing pathway of intersystem crossing (ISC), identifying the trimer Me-(DPH)$_3$ as the only oligomer exhibiting exclusively the desired SF pathways. Conversely, linear (DPH)$_3$ and (DPH)$_2$ show additional or exclusive triplet pathways via ISC. Our comprehensive analysis provides a detailed investigation into high-spin state formation, control, and emission in intramolecular singlet fission systems.

cond-mat.mtrl-sci↗

arXiv2024

Assessment of S* in the Orange Carotenoid Protein

The orange carotenoid protein (OCP) is the water-soluble mediator of non-photochemical quenching in cyanobacteria, a crucial photoprotective mechanism in response to excess illumination. OCP converts from a dark-adapted inactive state (OCPo) to an active quenching conformation (OCPr) under high-light conditions, resulting in a concomitant redshift in the absorption of the bound carotenoid. Here, we test whether a long-lived carotenoid singlet excited state (S*) is required for this photoconversion. We measured pump wavelength-dependent transient absorption of OCPo trapped in trehalose-sucrose glass films. We found that initial OCP photoproducts are still formed despite the glass preventing completion to OCPr, and that S* is only apparent for <495 nm pumps. By comparison to the pump wavelength-dependence of the OCPo to OCPr conversion in buffer, we show that S* is not required for photoconversion, and that S* likely arises from ground-state heterogeneity within OCPo.

physics.chem-ph↗

arXiv2022

Twisted carotenoids do not support efficient intramolecular singlet fission in the orange carotenoid protein

Singlet exciton fission is the spin-allowed generation of two triplet electronic excited states from a singlet state. Intramolecular singlet fission has been suggested to occur on individual carotenoid molecules within protein complexes, provided the conjugated backbone is twisted out-of-plane. However, this hypothesis has only been forwarded in protein complexes containing multiple carotenoids and bacteriochlorophylls in close contact. To test the hypothesis on twisted carotenoids in a 'minimal' one-carotenoid system, we study the orange carotenoid protein (OCP). OCP exists in two forms: in its orange form (OCPo), the single bound carotenoid is twisted, whereas in its red form (OCPr), the carotenoid is planar. To enable room-temperature spectroscopy on canthaxanthin-binding OCPo and OCPr without laser-induced photoconversion, we trap them in trehalose glass. Using transient absorption spectroscopy, we show that there is no evidence of long-lived triplet generation through intramolecular singlet fission, despite the canthaxanthin twist in OCPo.

physics.chem-ph↗

arXiv2019

Band-edge Excitation of Carotenoids Removes S* Revealing Triplet-pair Contributions to the S1 Absorption Spectrum

The nature of the low-lying electronic states in carotenoids has been debated for decades. We use excitation-dependent transient absorption spectroscopy and comparison with published results on \b{eta}-carotene to demonstrate that the so-called S* feature in astaxanthin, echinenone and spheroidenone spectra is due to an impurity in the sample. Excitation at the absorption band-edge results in a transient absorption spectrum dominated by the pure S1 photo-induced absorption, with no contribution from impurities (S*). We find that this S1 absorption resembles the triplet excited-state absorption spectrum, shifted by ~200meV. To explain this, we suggest that the individual triplets that make up the dominant triplet-pair (TT) configuration of 2A$_g^-$ contribute strongly to the S1 absorption band. Comparison with recent literature on molecular polycrystalline films which undergo singlet fission suggests the shift could be related to the binding energy of the triplet pair state. These findings have implications for understanding triplet-pair states in organic semiconductors and the excitation-energy dependence of singlet fission in carotenoid aggregates and biological systems.

physics.chem-ph↗

arXiv2018

Manipulating matter with strong coupling: harvesting triplet excitons in organic exciton microcavities

Exciton-polaritons are quasiparticles with mixed photon and exciton character that demonstrate rich quantum phenomena, novel optoelectronic devices and the potential to modify chemical properties of materials. Organic semiconductors are of current interest for their room-temperature polariton formation. However, within organic optoelectronic devices, it is often the 'dark' spin-1 triplet excitons that dominate operation. These triplets have been largely ignored in treatments of polariton physics. Here we demonstrate polariton population from the triplet manifold via triplet-triplet annihilation, leading to polariton emission that is longer-lived (>microseconds) even than exciton emission in bare films. This enhancement arises from spin-2 triplet-pair states, formed by singlet fission or triplet-triplet annihilation, feeding the polariton. This is possible due to state mixing, which -in the strong coupling regime- leads to sharing of photonic character with states that are formally non-emissive. Such 'photonic sharing' offers the enticing possibility of harvesting or manipulating even states that are formally dark.

cond-mat.mtrl-sci↗

arXiv2009

Determining exciton bandwidth and film microstructure in polythiophene films using linear absorption spectroscopy

We analyze the linear absorption spectrum of regioregular poly(3-hexylthiophene) films spun from a variety of solvents to probe directly the film microstructure and how it depends on processing conditions. We estimate the exciton bandwidth and the percentage of the film composed of aggregates quantitatively using a weakly interacting H-aggregate model. This provides a description of the degree and quality of crystallites within the film and is in turn correlated with thin-film field-effect transistor characteristics.

cond-mat.mtrl-sci↗

arXiv2007

The role of intermolecular coupling in the photophysics of disordered organic semiconductors: Aggregate emission in regioregular polythiophene

We address the role of excitonic coulping on the nature of photoexcitations in the conjugated polymer regioregular poly(3-hexylthiophene). By means of temperature-dependent absorption and photoluminescence spectroscopy, we show that optical emission is overwhelmingly dominated by weakly coupled H-aggregates. The relative absorbance of the 0-0 and 0-1 vibronic peaks provides a powerfully simple means to extract the magnitude of the intermolecular coupling energy, approximately 5 and 30 meV for films spun from isodurene and chloroform solutions respectively.

cond-mat.mtrl-sci↗