Excitation Energy Transfer between Non-Spherical Metal Nanoparticles:  Effects of Shape and Orientation on Distance Dependence of Transfer Rate

Saini, Sangeeta; Shenoy, Vijay B.; Bagchi, Biman

doi:10.1021/jp711197x

Cited by 15 publications

(25 citation statements)

References 27 publications

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“…[55] Many other generalizations of the theory have been published in the past three decades. [36,48,[56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73] It is notable that the Gersten-Nitzan theory as many of its generalizations represent the molecule as a classical dipole. vi This may appear strange considering the fact that the rate of spontaneous emission, an inherently quantum phenomenon, is obtained from this calculation.…”

Section: Dielectric Response Modelsmentioning

confidence: 99%

Optics of exciton-plasmon nanomaterials

Sukharev

Nitzan

2017

J. Phys.: Condens. Matter

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This review provides a brief introduction to the physics of coupled exciton-plasmon systems, the theoretical description and experimental manifestation of such phenomena, followed by an account of the state-of-the-art methodology for the numerical simulations of such phenomena and supplemented by a number of FORTRAN codes, by which the interested reader can introduce himself/herself to the practice of such simulations. Applications to CW light scattering as well as transient response and relaxation are described. Particular attention is given to so-called strong coupling limit, where the hybrid exciton-plasmon nature of the system response is strongly expressed. While traditional descriptions of such phenomena usually rely on analysis of the electromagnetic response of inhomogeneous dielectric environments that individually support plasmon and exciton excitations, here we explore also the consequences of a more detailed description of the molecular environment in terms of its quantum density matrix (applied in a mean field approximation level). Such a description makes it possible to account for characteristics that cannot be described by the dielectric response model: the effects of dephasing on the molecular response on one hand, and nonlinear response on the other. It also highlights the still missing important ingredients in the numerical approach, in particular its limitation to a classical description of the radiation field and its reliance on a mean field description of the many-body molecular system. We end our review with an outlook to the near future, where these limitations will be addressed and new novel applications of the numerical approach will be pursued.

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Section: Dielectric Response Modelsmentioning

confidence: 99%

Optics of exciton-plasmon nanomaterials

Sukharev

Nitzan

2017

J. Phys.: Condens. Matter

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“…The breakdown of the Forster rates in describing energy transfer in certain limits is well-documented, especially when the relevant transition densities are spatially distributed across a similar length scale to that of the donor/acceptor separation. 18,19 In this situation, a purely quantum-mechanical formalism is called for to describe the energy transfer process that is affordable enough to permit direct, time-domain simulations of the electronic dynamics and sufficiently accurate to capture the deviations from the dubious point-dipole approximations.In this report, we study the dynamical evolution of an exciton in a two silver nanowire array using first-principles electronic dynamics. We will focus on resolving the exciton decay and transfer rates and building a theoretical understanding of the mechanisms.…”

mentioning

confidence: 99%

Real-Time TDDFT Studies of Exciton Decay and Transfer in Silver Nanowire Arrays

et al. 2015

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Understanding dynamical characteristics of excited electronic states is crucial for rational design of functional nanomaterials. Using real-time time-dependent density functional theory, we present a fully quantum mechanical study on the transfer and decay of an exciton in an archetypal metal nanostructure. We introduce several approaches to analyze the dipole moment's time evolution to resolve exciton transfer rates and the pure dephasing times. These approaches are applied to studies of exciton diffusion length in a silver nanowire array. Calculated rates of polarization-induced transfer exhibit neither Forster's "sixth-power" dependence on donor− acceptor distance nor the perfect exponential separation dependence that typifies the Dexter transfer mechanism, suggesting that the nonperturbative, ab initio quantum dynamics captures intricacies of exciton transfer between quantized nanosystems that are beyond the reach of the canonical models of electronic energy transfer. ■ INTRODUCTIONExcitons, or Coulombically bound electron−hole pairs, are well-known to chemists, physicists, and material scientists alike as the quasiparticles (or elementary excitations) that result from coherent light−matter interactions and mediate most processes that occur in electronically excited states. These excitonic processes are the underlying driving forces in solar energy conversion and photocatalysis in inorganic 1−4 and molecular 5,6 semiconducting systems. Bound excitonic states also exist in metallic systems but are fleetingly short-lived owing to the rapid (sub-femtosecond) onset of Coulomb screening. 7,8 One route to prolonging the lifetime of excitonic states in conducting materials in order to enable some excitonically promoted physical process could be to utilize the quantized nature of nanosized metal clusters. Unlike their bulk/macroscopic counterparts, metal nanocrystals (e.g., nanowires) do not possess a dense band of delocalized states around the Fermi level. As a result, the photoexcited electron−hole pair can be long-lived due to the smaller resonant broadening of the excited state. Some of these long-lived excited states can even form coherent molecular plasmons as shown in previous work. 9−14 Underlying the potential of using the long-lived exciton in metal nanocrystals for energy research is the diffusion length of the exciton, i.e., the distance an exciton may travel prior to its complete decay. This important property determines the feasibility of harvesting the exciton for energy conversion and the engineering requirement of making a practical device. The exciton diffusion length is intrinsically related to the exciton transfer rate and the exciton decay time. However, due to its complex many-electron nature, calculating the exciton diffusion length from first principles has been a challenging task. Cao et al. have investigated energy transfer in perfect J-aggregates by associating excitons with Bloch states. 15 The analytical expression for the transfer rate they derive goes beyond the dipolar coupling model...

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“…This discrepancy between experimental observations and theoretical understanding has already been pointed out. [14][15][16][17] and the observed…”

Section: Introductionmentioning

confidence: 83%

“…The focus of the present paper is the phenomenon of energy transfer between an excited molecule and a nearby metal particle. This process has received considerable attention fueled by experimental observations of this phenomenon,(see 1,2 for early work and 3,4 for recent reviews) taken with a suitable theoretical analysis, [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] provide not only fundamental insight on the nature of molecular electronic relaxation near metal interfaces, but also a potential probe of the molecule-to-particle distance as well as the molecular orientation with respect to the particle surface; 12,[23][24][25][26][27][28][29][30] for a review see Ref. 4.…”

Section: Introductionmentioning

confidence: 99%

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Numerical Calculations of Radiative and Non-Radiative Relaxation of Molecules Near Metal Particles

2014

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The dependence of the radiative emission and the non-radiative (energy transfer to the metal) relaxation rates of a molecule near a small metal particle on the molecule-to-particle distance and on the molecular orientation is calculated using a numerical solution of the Maxwell equations for a model that described the metal as a dispersive dielectric particle and the molecule as an oscillating point dipole. The emission rate is obtained by evaluating the total oscillating dipole in the system, while the non-radiative rate is inferred from the rate of heat production on the particle. For the distance dependence of the non-radiative rate we find, in agreement with experimental observations, marked deviation from the prediction of the standard theory of fluorescence resonance energy transfer (FRET). In departure from previous interpretations, we find that electromagnetic retardation is the main source of this deviation at large moleculeparticle separations. The radiative emission rate reflects the total dipole induced in the moleculeparticle system, and its behavior as function of distance and orientation stems mostly from the magnitude of the oscillating polarization on the metal particle (which, at resonance, is strongly affected by plasmon excitation), and from the way this polarization combines with the molecular dipole to form the total system dipole.#" "

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Excitation Energy Transfer between Non-Spherical Metal Nanoparticles: Effects of Shape and Orientation on Distance Dependence of Transfer Rate

Cited by 15 publications

References 27 publications

Optics of exciton-plasmon nanomaterials

Optics of exciton-plasmon nanomaterials

Real-Time TDDFT Studies of Exciton Decay and Transfer in Silver Nanowire Arrays

Numerical Calculations of Radiative and Non-Radiative Relaxation of Molecules Near Metal Particles

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