arXiv subjects

Kuniyuki Miwa

Publications and source records attributed to Kuniyuki Miwa.

13 recordsLinked to original sources

arXiv2025

Single-molecule phosphorescence and intersystem crossing in a coupled exciton-plasmon system

Scanning the sharp metal tip of a scanning tunneling microscope (STM) over a molecule allows tuning the coupling between the tip plasmon and a molecular fluorescence emitter. This allows access to local variations of fluorescence field enhancement and wavelength shifts, which are central parameters for characterizing the plasmon-exciton coupling. Performing the same for phosphorescence with molecular scale resolution remains a significant challenge. In this study, we present the investigation of phosphorescence from isolated Pt-Phthalocyanine molecules by analyzing tip-enhanced emission spectra in both current-induced and laser-induced phosphorescence. The latter directly monitors singlet-to-triplet state intersystem crossing of a molecule below the tip. The study contributes to a detailed understanding of triplet excitation pathways and their potential control at sub-molecular length scales. Additionally, the coupling of organic phosphors to plasmonic structures is a promising route for improving light-emitting diodes.

cond-mat.mes-hall↗

arXiv2024

A coarse-grained description of anharmonic lattice environments affecting the quantum dynamics of charge carriers

Lattice softness has a significant impact on charge carrier dynamics in condensed matter systems, contributing to the emergence of various properties and functions. Examples include the remarkable carrier lifetimes and defect tolerances of hybrid organic-inorganic perovskites. Recent studies suggest the contribution of quartic anharmonicity of the lattice vibrations. The quartic anharmonicity can be discussed with a double-well potential, and the transition between the two minima can be coarse-grained as a two-state jump stochastic process. Such a stochastic approach is typically employed to describe dynamic fluctuations introduced into a system by two-state transitions in the surroundings. To investigate charge transport in materials, however, it is crucial to describe not only the fluctuations but also the dynamic lattice distortion associated with charge transport. Therefore, there is a need for a theory to describe the charge carrier dynamics proceeding alongside the lattice distortion dynamics. In this study, we present a theory that describes quantum dynamics under the influence of an environment with two stable states, termed a bistable environment. The theory describes the effects of fluctuations and dissipation induced from the bistable environment in a reasonable manner, and the effects exhibit a different temperature dependence than the widely employed Gaussian environment. The physical implication of this temperature dependence is provided in terms of the environmental dynamics. The results of this study are expected to provide a step forward in describing charge carrier dynamics in materials with lattice softness and pronounced lattice anharmonicity, e.g., hybrid organic-inorganic perovskites. Moreover, these findings represent an advancement in our understanding of and capacity to predict and control the physical properties and functions of these materials.

physics.chem-ph↗

arXiv2023

Probing exciton dynamics with spectral selectivity through the use of quantum entangled photons

Quantum light is increasingly recognized as a promising resource for developing optical measurement techniques. Particular attention has been paid to enhancing the precision of the measurements beyond classical techniques by using nonclassical correlations between quantum entangled photons. Recent advances in quantum optics technology have made it possible to manipulate the spectral and temporal properties of entangled photons, and the photon correlations can facilitate the extraction of matter information with relatively simple optical systems compared to conventional schemes. In these respects, the applications of entangled photons to time-resolved spectroscopy can open new avenues for unambiguously extracting information on dynamical processes in complex molecular and materials systems. Here, we propose time-resolved spectroscopy in which specific signal contributions are selectively enhanced by harnessing the nonclassical correlations of entangled photons. The entanglement time characterizes the mutual delay between an entangled twin and determines the spectral distribution of the photon correlations. The entanglement time plays a dual role as the knob for controlling the accessible time region of dynamical processes and the degrees of spectral selectivity. In this sense, the role of the entanglement time is substantially equivalent to the temporal width of the classical laser pulse. The results demonstrate that the application of quantum entangled photons to time-resolved spectroscopy leads to monitoring dynamical processes in complex molecular and materials systems by selectively extracting desired signal contributions from congested spectra. We anticipate that more elaborately engineered photon states would broaden the availability of quantum light spectroscopy.

physics.chem-ph↗

arXiv2022

Control and enhancement of single-molecule electroluminescence through strong light-matter coupling

The energetic positions of molecular electronic states at molecule/electrode interfaces are crucial factors for determining the transport and optoelectronic properties of molecular junctions. Strong light--matter coupling offers a potential for manipulating these factors, enabling to boost in the efficiency and versatility of these junctions. Here, we investigate electroluminescence from single-molecule junctions in which the molecule is strongly coupled with the vacuum electromagnetic field in a plasmonic nanocavity. We demonstrate an improvement in the electroluminescence efficiency by employing the strong light--matter coupling in conjunction with the characteristic feature of single-molecule junctions to selectively control the formation of the lowest-energy excited state. The mechanism of efficiency improvement is discussed based on the energetic position and composition of the formed polaritonic states. Our findings indicate the possibility to manipulate optoelectronic conversion in molecular junctions by strong light--matter coupling and contribute to providing design principles for developing efficient molecular optoelectronic devices.

cond-mat.mes-hall↗

arXiv2021

Quantum electrodynamics description of localized surface plasmons at a metal nanosphere

A canonical quantization scheme for localized surface plasmons (LSPs) in a metal nanosphere is presented based on a microscopic model composed of electromagnetic fields, oscillators that describe plasmons, and a reservoir that describes excitations other than plasmons. The eigenmodes of this fully quantum electrodynamic theory show a spectrum that includes radiative depolarization and broadening, including redshifting from the quasi-static LSP modes, with increasing particle size. These spectral profiles correctly match those obtained with exact classical electrodynamics (Mie theory). The present scheme provides the electric fields per plasmon in both near- and far-field regions whereby its utility in the fields of quantum plasmonics and nano-optics is demonstrated.

cond-mat.mes-hall↗

arXiv2019

Electronic friction in interacting systems

We consider effects of strong light-matter interaction on electronic friction in molecular junctions within generic model of single molecule nano cavity junction. Results of the Hubbard NEGF simulations are compared with mean-field NEGF and generalized Head-Gordon and Tully approaches. Mean-field NEGF is shown to fail qualitatively at strong intra-system interactions, while accuracy of the generalized Head-Gordon and Tully results is restricted to situations of well separated intra-molecular excitations, when bath induced coherences are negligible. Numerical results show effects of bias and cavity mode pumping on electronic friction. We demonstrate non-monotonic behavior of the friction on the bias and intensity of the pumping field and indicate possibility of engineering friction control in single molecule junctions.

cond-mat.mes-hall↗

arXiv2019

Hubbard NEGF Analysis of Photocurrent in Nitroazobenzene Molecular Junction

We present combined experimental and theoretical study of photo-induced current in molecular junctions consisting of monolayers of nitroazobenzene oligomers chemisorbed on carbon surfaces and illuminated by UV-Vis light through a transparent electrode. Experimentally observed dependence of the photocurrent on light frequency, temperature and monolayer thickness is analyzed within first principles simulations employing the Hubbard NEGF diagrammatic technique. We reproduce qualitatively correct behavior and discuss mechanisms leading to characteristic behavior of dark and photo-induced currents in response to changes in bias, frequency of radiation, temperature and thickness of molecular layer.

cond-mat.mes-hall↗

arXiv2018

Current-induced forces for nonadiabatic molecular dynamics

We present general first principles derivation of expression for current-induced forces. The expression is applicable in non-equilibrium molecular systems with arbitrary intra-molecular interactions and for any electron-nuclei coupling. It provides a controlled consistent way to account for quantum effects of nuclear motion, accounts for electronic non-Markov character of the friction tensor, and opens way to treatments beyond strictly adiabatic approximation. We show connection of the expression with previous studies, and discuss effective ways to evaluate the friction tensor.

cond-mat.mes-hall↗

arXiv2018

Towards Noise Simulation in Interacting Nonequilibrium Systems Strongly Coupled to Baths

Progress in experimental techniques at nanoscale made measurements of noise in molecular junctions possible. These data are important source of information not accessible through average flux measurements. Emergence of optoelectronics, recently shown possibility of strong light-matter couplings, and developments in the field of quantum thermodynamics are making counting statistics measurements of even higher importance. Theoretical methods for noise evaluation in first principles simulations can be roughly divided into approaches applicable in the case of weak intra-system interactions, and those treating strong interactions for systems weakly coupled to baths. We argue that due to structure of its diagrammatic expansion and the fact of utilizing many-body states as a basis of its formulation recently introduced nonequilibrium Hubbard Green functions formulation is a relatively inexpensive method suitable for evaluation of noise characteristics in first principles simulations over wide range of parameters. We illustrate viability of the approach by simulations of noise and noise spectrum within generic models for non-, weakly and strongly interacting systems. Results of the simulations are compared to exact data (where available) and to simulations performed within approaches best suited for each of the three parameter regimes.

cond-mat.mes-hall↗

arXiv2016

Orbital-selective single molecule excitation and spectroscopy based on plasmon-exciton coupling

The electronic excitation of molecules triggers diverse phenomena such as luminescence and photovoltaic effects, which are the bases of various energy-converting devices. Understanding and control of the excitations at the single-molecule level are long standing targets, however, they have been hampered by the limited spatial resolution in optical probing techniques. Here we investigate the electronic excitation of a single molecule with sub-molecular precision using a localised plasmon at the tip apex of a scanning tunnelling microscope (STM) as an excitation probe. Coherent energy transfer between the plasmon and molecular excitons is discovered when the plasmon is located in the proximity of isolated molecules, which is corroborated by a theoretical analysis. The polarised plasmonic field enables selective excitation of an electronic transition between anisotropic frontier molecular orbitals. Our findings have established the foundation of a novel single-molecule spectroscopy with STM, providing an integrated platform for real-space investigation of localised excited states.

physics.chem-ph↗

arXiv2014

Energy dissipation of electrons at a p-type GaAs(110) surface

Electron injection from the tip of a scanning tunneling microscope into a p-type GaAs(110) surface have been used to induce luminescence in the bulk. Atomically-resolved photon maps revealed significant reduction of luminescence intensity at surface states localized near Ga atoms. Quantitative analysis based on the first principles calculation and a rate equation approach was performed to describe overall energy dissipation processes of the incident tunneling electrons. Our study shows that the recombination processes in the bulk electronic states are suppressed by the fast electron scattering at the surface, and the electrons dominantly undergo non-radiative recombination through the surface states.

cond-mat.mes-hall↗

arXiv2013

Interplay between Plasmon Luminescence and Vibrationally Resolved Molecular Luminescence Induced by Scanning Tunneling Microscopy

Effects of coupling between a molecular exciton and a surface plasmon (exciton-plasmon coupling) on the luminescence properties of the molecule and the surface plasmons are investigated using the nonequilibrium Green's function method. Molecular absorption and enhancement by molecular electronic and vibrational modes (molecular modes) lead to dip and peak structures in the luminescence spectra of the surface plasmons. These structures will correspond to the peak and dip structures observed in a recent experiment. We found that in addition to the molecular dynamics, the re-absorption by the surface plasmons plays important roles in determining the luminescence spectral profiles.

cond-mat.mtrl-sci↗

arXiv2013

Effects of Interference between Energy Absorption Processes of Molecule and Surface Plasmons on Light Emission Induced by Scanning Tunneling Microscopy

Effects of coupling between an molecular exciton and a surface plasmon (exciton-plasmon coupling) on the luminescence properties of the molecule and the surface plasmons are investigated using nonequilibrium Green's function method. Molecular absorption and enhancement by molecular electronic and vibrational modes (molecular modes) lead to dip and peak structures in the luminescence spectra of the surface plasmons. The re-absorption by the surface plasmons leads to a dent structure in their luminescence spectra. It is found that the processes of the molecular absorption and the re-absorption by the surface plasmons interfere with each other. Enhancement and suppression of these energy-absorption processes are due to the interference. Moreover, due to the exciton-plasmon coupling, excitation channels of the molecule arise in the energy range lower than the first electronic excitation energy of the molecule. It is found that the electron transitions via these excitation channels give rise to the molecular luminescence and the vibrational excitations at the bias voltage lower than the ratio of the first electronic excitation energy of the molecule to the elementary charge. The results also indicate that the vibrational excitations assist the emission of photons, whose energy exceeds the product of the elementary charge and the bias voltage (upconverted luminescence).

cond-mat.mtrl-sci↗