Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 21
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Nat Nanotechnol ; 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-33649585

RESUMO

Theoretical studies suggest that mastering the thermocurrent through single molecules can lead to thermoelectric energy harvesters with unprecedentedly high efficiencies.1-6 This can be achieved by engineering molecule length,7 optimizing the tunnel coupling strength of molecules via chemical anchor groups8 or by creating localized states in the backbone with resulting quantum interference features.4 Empirical verification of these predictions, however, faces considerable experimental challenges and is still awaited. Here we use a novel measurement protocol that simultaneously probes the conductance and thermocurrent flow as a function of bias voltage and gate voltage. We find that the resulting thermocurrent is strongly asymmetric with respect to the gate voltage, with evidence of molecular excited states in the thermocurrent Coulomb diamond maps. These features can be reproduced by a rate-equation model only if it accounts for both the vibrational coupling and the electronic degeneracies, thus giving direct insight into the interplay of electronic and vibrational degrees of freedom, and the role of spin entropy in single molecules. Overall these results show that thermocurrent measurements can be used as a spectroscopic tool to access molecule-specific quantum transport phenomena.

2.
Sci Rep ; 11(1): 4281, 2021 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-33608609

RESUMO

Systems of interacting charges and fields are ubiquitous in physics. Recently, it has been shown that Hamiltonians derived using different gauges can yield different physical results when matter degrees of freedom are truncated to a few low-lying energy eigenstates. This effect is particularly prominent in the ultra-strong coupling regime. Such ambiguities arise because transformations reshuffle the partition between light and matter degrees of freedom and so level truncation is a gauge dependent approximation. To avoid this gauge ambiguity, we redefine the electromagnetic fields in terms of potentials for which the resulting canonical momenta and Hamiltonian are explicitly unchanged by the gauge choice of this theory. Instead the light/matter partition is assigned by the intuitive choice of separating an electric field between displacement and polarisation contributions. This approach is an attractive choice in typical cavity quantum electrodynamics situations.

3.
J Chem Phys ; 153(13): 134701, 2020 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-33032411

RESUMO

We present a novel, counter-intuitive method, based on dark-state protection, for significantly improving exciton transport efficiency through "wires" comprising a chain of molecular sites with an intrinsic energy gradient. Specifically, by introducing "barriers" to the energy landscape at regular intervals along the transport path, we find that undesirable radiative recombination processes are suppressed due to a clear separation of sub-radiant and super-radiant eigenstates in the system. This, in turn, can lead to an improvement in transmitted power by many orders of magnitude, even for very long chains. From there, we analyze the robustness of this phenomenon to changes in both system and environment properties to show that this effect can be beneficial over a range of different thermal and optical environment regimes. Finally, we show that the novel energy landscape presented here may provide a useful foundation for overcoming the short length scales over which exciton diffusion typically occurs in organic photo-voltaics and other nanoscale transport scenarios, thus leading to considerable potential improvements in the efficiency of such devices.

4.
J R Soc Interface ; 17(169): 20200399, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32842892

RESUMO

The iron stress-induced protein A (IsiA) is a source of interest and debate in biological research. The IsiA supercomplex, binding over 200 chlorophylls, assembles in multimeric rings around photosystem I (PSI). Recently, the IsiA-PSI structure from Synechocystis sp. PCC 6803 was resolved to 3.48 Å. Based on this structure, we created a model simulating a single excitation event in an IsiA monomer. This model enabled us to calculate the fluorescence and the localization of the excitation in the IsiA structure. To further examine this system, noise was introduced to the model in two forms-thermal and positional. Introducing noise highlights the functional differences in the system between cryogenic temperatures and biologically relevant temperatures. Our results show that the energetics of the IsiA pigment-protein complex are very robust at room temperature. Nevertheless, shifts in the position of specific chlorophylls lead to large changes in their optical and fluorescence properties. Based on these results, we discuss the implication of highly robust structures, with potential for serving different roles in a context-dependent manner, on our understanding of the function and evolution of photosynthetic processes.

5.
J Chem Phys ; 152(6): 064103, 2020 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-32061212

RESUMO

Marcus and Landauer-Büttiker approaches to charge transport through molecular junctions describe two contrasting mechanisms of electronic conduction. In previous work, we have shown how these charge transport theories can be unified in the single-level case by incorporating lifetime broadening into the second-order quantum master equation. Here, we extend our previous treatment by incorporating lifetime broadening in the spirit of the self-consistent Born approximation. By comparing both theories to numerically converged hierarchical-equations-of-motion results, we demonstrate that our novel self-consistent approach rectifies shortcomings of our earlier framework, which are present especially in the case of relatively strong electron-vibrational coupling. We also discuss circumstances under which the theory developed here simplifies to the generalized theory developed in our earlier work. Finally, by considering the high-temperature limit of our new self-consistent treatment, we show how lifetime broadening can also be self-consistently incorporated into Marcus theory. Overall, we demonstrate that the self-consistent approach constitutes a more accurate description of molecular conduction while retaining most of the conceptual simplicity of our earlier framework.

7.
Nat Commun ; 10(1): 4628, 2019 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-31604934

RESUMO

Off-resonant charge transport through molecular junctions has been extensively studied since the advent of single-molecule electronics and 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 non-interacting Landauer theory as well as the conventional single-mode Franck-Condon model. Instead, we model overall charge transport as a sequence of non-adiabatic electron transfers, with rates depending 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 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.

8.
Nanoscale ; 11(31): 14820-14827, 2019 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-31355401

RESUMO

The electronic and magnetic properties of single-molecule transistors depend critically on the molecular charge state. Charge transport in single-molecule transistors is characterized by Coulomb-blocked regions in which the charge state of the molecule is fixed and current is suppressed, separated by high-conductance, sequential-tunneling regions. It is often difficult to assign the charge state of the molecular species in each Coulomb-blocked region due to variability in the work-function of the electrodes. In this work, we provide a simple and fast method to assign the charge state of the molecular species in the Coulomb-blocked regions based on signatures of electron-phonon coupling together with the Pauli-exclusion principle, simply by observing the asymmetry in the current in high-conductance regions of the stability diagram. We demonstrate that charge-state assignments determined in this way are consistent with those obtained from measurements of Zeeman splittings. Our method is applicable at 77 K, in contrast to magnetic-field-dependent measurements, which generally require low temperatures (below 4 K). Due to the ubiquity of electron-phonon coupling in molecular junctions, we expect this method to be widely applicable to single-electron transistors based on single molecules and graphene quantum dots. The correct assignment of charge states allows researchers to better understand the fundamental charge-transport properties of single-molecule transistors.

9.
J Chem Phys ; 149(15): 154112, 2018 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-30342434

RESUMO

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.

10.
Sci Adv ; 4(5): eaap9416, 2018 05.
Artigo em Inglês | MEDLINE | ID: mdl-29736414

RESUMO

When two indistinguishable photons are each incident on separate input ports of a beamsplitter, they "bunch" deterministically, exiting via the same port as a direct consequence of their bosonic nature. This two-photon interference effect has long-held the potential for application in precision measurement of time delays, such as those induced by transparent specimens with unknown thickness profiles. However, the technique has never achieved resolutions significantly better than the few-femtosecond (micrometer) scale other than in a common-path geometry that severely limits applications. We develop the precision of Hong-Ou-Mandel interferometry toward the ultimate limits dictated by statistical estimation theory, achieving few-attosecond (or nanometer path length) scale resolutions in a dual-arm geometry, thus providing access to length scales pertinent to cell biology and monoatomic layer two-dimensional materials.

11.
J Phys Chem Lett ; 9(8): 1859-1865, 2018 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-29589450

RESUMO

The quest for molecular structures exhibiting strong quantum interference effects in the transport setting has long been on the forefront of chemical research. We establish theoretically that the unusual geometry of spiro-conjugated systems gives rise to complete destructive interference in the resonant-transport regime. This results in a current blockade of the type not present in meta-connected benzene or similar molecular structures. We further show that these systems can undergo a transport-driven Jahn-Teller distortion, which can lift the aforementioned destructive-interference effects. The overall transport characteristics are determined by the interplay between the two phenomena. Spiro-conjugated systems may therefore serve as a novel platform for investigations of quantum interference and vibronic effects in the charge-transport setting. The potential to control quantum interference in these systems can also turn them into attractive components in designing functional molecular circuits.

12.
Phys Chem Chem Phys ; 19(43): 29534-29539, 2017 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-29082390

RESUMO

Single-molecule electronics has been envisioned as the ultimate goal in the miniaturisation of electronic circuits. While the aim of incorporating single-molecule junctions into modern technology still proves elusive, recent developments in this field have begun to enable experimental investigation of fundamental concepts within the area of chemical physics. One such phenomenon is the concept of environment-assisted quantum transport which has emerged from the investigation of exciton transport in photosynthetic complexes. Here, we study charge transport through a two-site molecular junction coupled to a vibrational environment. We demonstrate that vibrational interactions can significantly enhance the current through specific molecular orbitals. Our study offers a clear pathway towards finding and identifying environment-assisted transport phenomena in charge transport settings.

13.
Phys Rev Lett ; 117(20): 203603, 2016 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-27886483

RESUMO

Conventional photocells suffer a fundamental efficiency threshold imposed by the principle of detailed balance, reflecting the fact that good absorbers must necessarily also be fast emitters. This limitation can be overcome by "parking" the energy of an absorbed photon in a dark state which neither absorbs nor emits light. Here we argue that suitable dark states occur naturally as a consequence of the dipole-dipole interaction between two proximal optical dipoles for a wide range of realistic molecular dimers. We develop an intuitive model of a photocell comprising two light-absorbing molecules coupled to an idealized reaction center, showing asymmetric dimers are capable of providing a significant enhancement of light-to-current conversion under ambient conditions. We conclude by describing a road map for identifying suitable molecular dimers for demonstrating this effect by screening a very large set of possible candidate molecules.

14.
Sci Rep ; 6: 28204, 2016 06 23.
Artigo em Inglês | MEDLINE | ID: mdl-27335176

RESUMO

Understanding the dynamics of higher-dimensional quantum systems embedded in a complex environment remains a significant theoretical challenge. While several approaches yielding numerically converged solutions exist, these are computationally expensive and often provide only limited physical insight. Here we address the question: when do more intuitive and simpler-to-compute second-order perturbative approaches provide adequate accuracy? We develop a simple analytical criterion and verify its validity for the case of the much-studied FMO dynamics as well as the canonical spin-boson model.

16.
Phys Rev Lett ; 110(10): 100503, 2013 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-23521240

RESUMO

Coupled spin chains are promising candidates for wiring up qubits in solid-state quantum computing (QC). In particular, two nitrogen-vacancy centers in diamond can be connected by a chain of implanted nitrogen impurities; when driven by suitable global fields the chain can potentially enable quantum state transfer at room temperature. However, our detailed analysis of error effects suggests that foreseeable systems may fall far short of the fidelities required for QC. Fortunately the chain can function in the more modest role as a mediator of noisy entanglement, enabling QC provided that we use subsequent purification. For instance, a chain of 5 spins with interspin distances of 10 nm has finite entangling power as long as the T(2) time of the spins exceeds 0.55 ms. Moreover we show that repurposing the chain this way can remove the restriction to nearest-neighbor interactions, so eliminating the need for complicated dynamical decoupling sequences.

17.
Biophys J ; 102(5): 961-8, 2012 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-22404918

RESUMO

Certain migratory birds can sense the Earth's magnetic field. The nature of this process is not yet properly understood. Here we offer a simple explanation according to which birds literally see the local magnetic field through the impact of a physical rather than a chemical signature of the radical pair: a transient, long-lived electric dipole moment. Based on this premise, our picture can explain recent surprising experimental data indicating long lifetimes for the radical pair. Moreover, there is a clear evolutionary path toward this field-sensing mechanism: it is an enhancement of a weak effect that may be present in many species.


Assuntos
Campos Magnéticos , Modelos Biológicos , Migração Animal/fisiologia , Migração Animal/efeitos da radiação , Radicais Livres/metabolismo , Ondas de Rádio , Fatores de Tempo
18.
Nat Commun ; 3: 606, 2012 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-22215081

RESUMO

The quantum superposition principle states that an entity can exist in two different states simultaneously, counter to our 'classical' intuition. Is it possible to understand a given system's behaviour without such a concept? A test designed by Leggett and Garg can rule out this possibility. The test, originally intended for macroscopic objects, has been implemented in various systems. However to date no experiment has employed the 'ideal negative result' measurements that are required for the most robust test. Here we introduce a general protocol for these special measurements using an ancillary system, which acts as a local measuring device but which need not be perfectly prepared. We report an experimental realization using spin-bearing phosphorus impurities in silicon. The results demonstrate the necessity of a non-classical picture for this class of microscopic system. Our procedure can be applied to systems of any size, whether individually controlled or in a spatial ensemble.

19.
Phys Rev Lett ; 107(20): 207210, 2011 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-22181771

RESUMO

Recently there have been several theoretical and experimental studies of the prospects for magnetic field sensors based on crystal defects, especially nitrogen vacancy (NV) centers in diamond. Such systems could potentially be incorporated into an atomic force microscopy-like apparatus in order to map the magnetic properties of a surface at the single spin level. In this Letter we propose an augmented sensor consisting of an NV center for readout and an "amplifier" spin system that directly senses the local magnetic field. Our calculations show that this hybrid structure has the potential to detect magnetic moments with a sensitivity and spatial resolution far beyond that of a simple NV center, and indeed this may be the physical limit for sensors of this class.


Assuntos
Fenômenos Magnéticos , Nitrogênio/química , Prótons
20.
Phys Rev Lett ; 106(11): 110504, 2011 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-21469852

RESUMO

Electron spin qubits in molecular systems offer high reproducibility and the ability to self-assemble into larger architectures. However, interactions between neighboring qubits are "always on," and although the electron spin coherence times can be several hundred microseconds, these are still much shorter than typical times for nuclear spins. Here we implement an electron-nuclear hybrid scheme which uses coherent transfer between electron and nuclear spin degrees of freedom in order to both effectively turn on or off interqubit coupling mediated by dipolar interactions and benefit from the long nuclear spin decoherence times (T(2n)). We transfer qubit states between the electron and (15)N nuclear spin in (15)N@C(60) with a two-way process fidelity of 88%, using a series of tuned microwave and radio frequency pulses and measure a nuclear spin coherence lifetime of over 100 ms.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...