72 research outputs found

    Marcus Theory of Thermoelectricity in Molecular Junctions

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    Thermoelectric energy conversion is perhaps the most promising of the potential applications of molecular electronics. Ultimately, it is desirable for this technology to operate at around room temperature, and it is therefore important to consider the role of dissipative effects in these conditions. Here, we develop a theory of thermoelectricity which accounts for the vibrational coupling within the framework of Marcus theory. We demonstrate that the inclusion of lifetime broadening is necessary in the theoretical description of this phenomenon. We further show that the Seebeck coefficient and the power factor decrease with increasing reorganisation energy, and identify the optimal operating conditions in the case of non-zero reorganisation energy. Finally, with the aid of DFT calculations, we consider a prototypical fullerene-based molecular junction. We estimate the maximum power factor that can be obtained in this system, and confirm that C60_{60} is an excellent candidate for thermoelectric heat-to-energy conversion. This work provides general guidance that should be followed in order to achieve high-efficiency molecular thermoelectric materials.Comment: Supporting Information available at https://doi.org/10.1021/acs.jpcc.8b1216

    Beyond Marcus theory and the Landauer-Büttiker approach in molecular junctions: A unified framework.

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    Charge transport through molecular junctions is often described either as a purely coherent or a purely classical phenomenon, and described using the Landauer-Büttiker formalism or Marcus theory (MT), respectively. Using a generalised quantum master equation, we here derive an expression for current through a molecular junction modelled as a single electronic level coupled with a collection of thermalised vibrational modes. We demonstrate that the aforementioned theoretical approaches can be viewed as two limiting cases of this more general expression and present a series of approximations of this result valid at higher temperatures. We find that MT is often insufficient in describing the molecular charge transport characteristics and gives rise to a number of artefacts, especially at lower temperatures. Alternative expressions, retaining its mathematical simplicity, but rectifying those shortcomings, are suggested. In particular, we show how lifetime broadening can be consistently incorporated into MT, and we derive a low-temperature correction to the semi-classical Marcus hopping rates. Our results are applied to examples building on phenomenological as well as microscopically motivated electron-vibrational coupling. We expect them to be particularly useful in experimental studies of charge transport through single-molecule junctions as well as self-assembled monolayers

    Distinguishing Lead and Molecule States in Graphene-Based Single-Electron Transistors

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    Graphene provides a two-dimensional platform for contacting individual molecules, which enables transport spectroscopy of molecular orbital, spin and vibrational states. Here we report single-electron tunneling through a molecule that has been anchored to two graphene leads. Quantum interference within the graphene leads gives rise to an energy-dependent transmission and fluctuations in the sequential tunnel-rates. The lead states are electrostatically tuned by a global back-gate, resulting in a distinct pattern of varying intensity in the measured conductance maps. This pattern could potentially obscure transport features that are intrinsic to the molecule under investigation. Using ensemble averaged magneto-conductance measurements, lead and molecule states are disentangled, enabling spectroscopic investigation of the single molecule

    Understanding resonant charge transport through weakly coupled single-molecule junctions

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    Off-resonant charge transport through molecular junctions has been extensively studied since the advent of single-molecule electronics and it is now well understood within the framework of the non-interacting Landauer approach. Conversely, gaining a qualitative and quantitative understanding of the resonant transport regime has proven more elusive. Here, we study resonant charge transport through graphene-based zinc-porphyrin junctions. We experimentally demonstrate an inadequacy of the non-interacting Landauer theory as well as the conventional single-mode Franck-Condon model. Instead, we model the overall charge transport as a sequence of non-adiabatic electron transfers, the rates of which depend on both outer and inner-sphere vibrational interactions. We show that the transport properties of our molecular junctions are determined by a combination of electron-electron and electron-vibrational coupling, and are sensitive to the interactions with the wider local environment. Furthermore, we assess the importance of nuclear tunnelling and examine the suitability of semi-classical Marcus theory as a description of charge transport in molecular devices.Comment: version accepted in Nature Communications; SI available at https://researchportal.hw.ac.uk/en/publications/understanding-resonant-charge-transport-through-weakly-coupled-s

    Understanding resonant charge transport through weakly coupled single-molecule junctions

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    Off-resonant charge transport through molecular junctions has been extensively studied since the advent of single-molecule electronics and it is now well understood within the framework of the non-interacting Landauer approach. Conversely, gaining a qualitative and quantitative understanding of the resonant transport regime has proven more elusive. Here, we study resonant charge transport through graphene-based zinc-porphyrin junctions. We experimentally demonstrate an inadequacy of the non-interacting Landauer theory as well as the conventional single-mode Franck-Condon model. Instead, we model the overall charge transport as a sequence of non-adiabatic electron transfers, the rates of which depend on both outer and inner-sphere vibrational interactions. We show that the transport properties of our molecular junctions are determined by a combination of electron-electron and electron-vibrational coupling, and are sensitive to the interactions with the wider local environment. Furthermore, we assess the importance of nuclear tunnelling and examine the suitability of semi-classical Marcus theory as a description of charge transport in molecular devices.Comment: version accepted in Nature Communications; SI available at https://researchportal.hw.ac.uk/en/publications/understanding-resonant-charge-transport-through-weakly-coupled-s

    Optical coherence tomography—current technology and applications in clinical and biomedical research

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    X-exome sequencing of 405 unresolved families identifies seven novel intellectual disability genes

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    X-linked intellectual disability (XLID) is a clinically and genetically heterogeneous disorder. During the past two decades in excess of 100 X-chromosome ID genes have been identified. Yet, a large number of families mapping to the X-chromosome remained unresolved suggesting that more XLID genes or loci are yet to be identified. Here, we have investigated 405 unresolved families with XLID. We employed massively parallel sequencing of all X-chromosome exons in the index males. The majority of these males were previously tested negative for copy number variations and for mutations in a subset of known XLID genes by Sanger sequencing. In total, 745 X-chromosomal genes were screened. After stringent filtering, a total of 1297 non-recurrent exonic variants remained for prioritization. Co-segregation analysis of potential clinically relevant changes revealed that 80 families (20%) carried pathogenic variants in established XLID genes. In 19 families, we detected likely causative protein truncating and missense variants in 7 novel and validated XLID genes (CLCN4, CNKSR2, FRMPD4, KLHL15, LAS1L, RLIM and USP27X) and potentially deleterious variants in 2 novel candidate XLID genes (CDK16 and TAF1). We show that the CLCN4 and CNKSR2 variants impair protein functions as indicated by electrophysiological studies and altered differentiation of cultured primary neurons from Clcn4−/− mice or after mRNA knock-down. The newly identified and candidate XLID proteins belong to pathways and networks with established roles in cognitive function and intellectual disability in particular. We suggest that systematic sequencing of all X-chromosomal genes in a cohort of patients with genetic evidence for X-chromosome locus involvement may resolve up to 58% of Fragile X-negative cases

    Molecular mechanism of the TP53-MDM2-AR-AKT signalling network regulation by USP12

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    The TP53-MDM2-AR-AKT signalling network plays a critical role in the development and progression of prostate cancer. However, the molecular mechanisms regulating this signalling network are not completely defined. By conducting transcriptome analysis, denaturing immunoprecipitations and immunopathology, we demonstrate that the TP53-MDM2-AR-AKT cross-talk is regulated by the deubiquitinating enzyme USP12 in prostate cancer. Our findings explain why USP12 is one of the 12 most commonly overexpressed cancer-associated genes located near an amplified super-enhancer. We find that USP12 deubiquitinates MDM2 and AR, which in turn controls the levels of the TP53 tumour suppressor and AR oncogene in prostate cancer. Consequently, USP12 levels are predictive not only of cancer development but also of patient’s therapy resistance, relapse and survival. Therefore, our findings suggest that USP12 could serve as a promising therapeutic target in currently incurable castrate-resistant prostate cancer

    Vibrational effects in quantum transport through single-molecule junctions

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    This thesis is concerned with vibrational effects in resonant charge transport through molecular junctions. The first research chapter examines the role of non-equilibrium vibrational dynamics in charge transport through a molecular double quantum dot. We demonstrate that non-equilibrium vibrational effects in such a system can result in current suppression and negative differential conductance. The second research chapter describes how vibrational dynamics can be incorporated into the theoretical description of molecular junctions based on a Pariser-Parr-Pople Hamiltonian. As a case study, we consider a prototypical spiro-conjugated molecular junction. We demonstrate that the transport properties of this system are governed by an interplay between destructive quantum interference and Jahn-Teller distortion (an effect of vibronic origin). In the next chapter, we examine the role of collective vibrational coupling in charge transport through a two-site molecular system akin to the one considered in the first research chapter. We demonstrate that such interactions can significantly enhance the efficiency of transport through such a system, and also take this opportunity to analyse various theoretical descriptions of electron-vibrational interactions commonly used in the transport setting. In the fourth research chapter, we consider a single-site molecular system coupled to a collection of thermalised vibrational modes. We formulate a relatively simple yet powerful theoretical framework describing charge transport through such a system. We recover the Marcus and Landauer-Buttiker theories of transport in the limit of high-temperature and vanishing electron-vibrational coupling, respectively. We further show how lifetime broadening can be consistently incorporated into Marcus theory, and we derive a low-temperature correction to the semi-classical Marcus hopping rates. In the last research chapter, elements of this framework are applied to experimental measurements of charge transport through zinc-porphyrin molecular junctions. This joint experimental-theoretical study provides, for the first time, a full understanding of the resonant transport regime of graphene-based molecular junctions.</p
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