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Journal ArticleDOI

Expanded Theory of H- and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer.

17 Apr 2018-Chemical Reviews (American Chemical Society)-Vol. 118, Iss: 15, pp 7069-7163
TL;DR: This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated.
Abstract: The electronic excited states of molecular aggregates and their photophysical signatures have long fascinated spectroscopists and theoreticians alike since the advent of Frenkel exciton theory almost 90 years ago. The influence of molecular packing on basic optical probes like absorption and photoluminescence was originally worked out by Kasha for aggregates dominated by Coulombic intermolecular interactions, eventually leading to the classification of J- and H-aggregates. This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated. An assortment of packing geometries is considered from the humble molecular dimer to more exotic structures including linear and bent aggregates, two-dimensional herringbone and “HJ” aggregates, and chiral aggregates. The interplay between long-range Coulomb coupling and short-range charge-transfer-mediated coupling strongly depends on the aggregate ...
Citations
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Journal ArticleDOI
TL;DR: This Essay discusses the AIE phenomenon from a broader perspective, with an emphasis on early observations related to AIE made long before the term was coined, with a focus on cyanine dyes such as thiazole orange or its dimers.
Abstract: Aggregation-induced emission (AIE) has attracted considerable interest over the last twenty years. In contrast to the large number of available reviews focusing specifically on AIE, this Essay discusses the AIE phenomenon from a broader perspective, with an emphasis on early observations related to AIE made long before the term was coined. Illustrative examples are highlighted from the 20th century where fluorescence enhancement upon rigidification of dyes in viscous or solid environments or J-aggregate formation was studied. It is shown that these examples already include typical AIE luminogens such as tetraphenylethylene (TPE) as well as stilbenes and oligo- or polyphenylenevinylenes and -ethynylenes, which became important fluorescent solid-state materials in OLED research in the 1990s. Further examples include cyanine dyes such as thiazole orange (TO) or its dimers (TOTOs), which have been widely applied as molecular probes in nucleic acid research. The up to 10 000-fold fluorescence enhancement of such dyes upon intercalation into double-stranded DNA, attributable to the restricted intramolecular motion (RIM) concept, afforded commercial products for bioimaging and fluorescence sensing applications already in the early 1990s.

291 citations

Journal ArticleDOI
TL;DR: This Review will describe recent theoretical advances including treatment of electronic decoherence in surface-hopping methods, the role of solvent effects, trivial unavoided crossings, analysis of data based on transition densities, and efficient computational implementations of these numerical methods.
Abstract: Optically active molecular materials, such as organic conjugated polymers and biological systems, are characterized by strong coupling between electronic and vibrational degrees of freedom. Typically, simulations must go beyond the Born-Oppenheimer approximation to account for non-adiabatic coupling between excited states. Indeed, non-adiabatic dynamics is commonly associated with exciton dynamics and photophysics involving charge and energy transfer, as well as exciton dissociation and charge recombination. Understanding the photoinduced dynamics in such materials is vital to providing an accurate description of exciton formation, evolution, and decay. This interdisciplinary field has matured significantly over the past decades. Formulation of new theoretical frameworks, development of more efficient and accurate computational algorithms, and evolution of high-performance computer hardware has extended these simulations to very large molecular systems with hundreds of atoms, including numerous studies of organic semiconductors and biomolecules. In this Review, we will describe recent theoretical advances including treatment of electronic decoherence in surface-hopping methods, the role of solvent effects, trivial unavoided crossings, analysis of data based on transition densities, and efficient computational implementations of these numerical methods. We also emphasize newly developed semiclassical approaches, based on the Gaussian approximation, which retain phase and width information to account for significant decoherence and interference effects while maintaining the high efficiency of surface-hopping approaches. The above developments have been employed to successfully describe photophysics in a variety of molecular materials.

221 citations

Journal ArticleDOI
TL;DR: In this article, a review of machine learning for excited states of molecules is presented, focusing on not only how machine learning is employed to speed up such excited-state simulations but also how this branch of artificial intelligence can be used to advance this exciting research field in all its aspects.
Abstract: Electronically excited states of molecules are at the heart of photochemistry, photophysics, as well as photobiology and also play a role in material science. Their theoretical description requires highly accurate quantum chemical calculations, which are computationally expensive. In this review, we focus on not only how machine learning is employed to speed up such excited-state simulations but also how this branch of artificial intelligence can be used to advance this exciting research field in all its aspects. Discussed applications of machine learning for excited states include excited-state dynamics simulations, static calculations of absorption spectra, as well as many others. In order to put these studies into context, we discuss the promises and pitfalls of the involved machine learning techniques. Since the latter are mostly based on quantum chemistry calculations, we also provide a short introduction into excited-state electronic structure methods and approaches for nonadiabatic dynamics simulations and describe tricks and problems when using them in machine learning for excited states of molecules.

194 citations

Journal ArticleDOI
TL;DR: It is reported that the hole transfer channel of photocharge generation is mediated by an intra-moiety excited state in a blend of donor polymer PM6 and NFA Y6 using broadband transient absorption (TA) spectroscopy, suggesting that manipulating the interplay between intra-Moiety and interfacial excited species can provide a promising route for further improving device performance.
Abstract: Bulk-heterojunction organic photovoltaic devices with nonfullerene acceptors (NFAs) exhibit efficient hole transfer with small interfacial energy offset, which results in power conversion efficiencies above 17% in single junction devices using the high-performance NFA of Y6. However, the underlying mechanism responsible for the hole transfer channel in the polymer/Y6 blends remains poorly understood. Herein, we report that the hole transfer channel of photocharge generation is mediated by an intra-moiety excited state in a blend of donor polymer PM6 and NFA Y6 using broadband transient absorption (TA) spectroscopy. By comparing the TA data recorded from the solution and film Y6 samples, we identify the ultrafast formation of an intra-moiety excimer state together with the conversion from the primary local excitation on a time scale of ∼0.2 ps in the Y6 film. The intra-moiety excimer state acts as the intermediate for the hole transfer channel, which dissociates into free polarons on a time scale of ∼15 ps in the PM6/Y6 blend at room temperature. The intra-moiety intermediate state, arising from the intermolecular coupling in Y6 domains, is markedly different from the interfacial charge transfer state, which is commonly accepted as the intermediate state for the electron transfer channel. These findings suggest that manipulating the interplay between intra-moiety and interfacial excited species can provide a promising route for further improving device performance.

174 citations

Journal ArticleDOI
TL;DR: The basic physical principles and consequences of strong light-matter coupling common to molecular ensembles embedded in UV-visible or infrared cavities are described and the competition between the collective cooperative dipolar response of a molecular ensemble and local dynamical processes that molecules typically undergo are discussed.
Abstract: This is a tutorial-style introduction to the field of molecular polaritons. We describe the basic physical principles and consequences of strong light-matter coupling common to molecular ensembles embedded in UV-visible or infrared cavities. Using a microscopic quantum electrodynamics formulation, we discuss the competition between the collective cooperative dipolar response of a molecular ensemble and local dynamical processes that molecules typically undergo, including chemical reactions. We highlight some of the observable consequences of this competition between local and collective effects in linear transmission spectroscopy, including the formal equivalence between quantum mechanical theory and the classical transfer matrix method, under specific conditions of molecular density and indistinguishability. We also overview recent experimental and theoretical developments on strong and ultrastrong coupling with electronic and vibrational transitions, with a special focus on cavity-modified chemistry and infrared spectroscopy under vibrational strong coupling. We finally suggest several opportunities for further studies that may lead to novel applications in chemical and electromagnetic sensing, energy conversion, optoelectronics, quantum control, and quantum technology.

141 citations


Cites background from "Expanded Theory of H- and J-Molecul..."

  • ...These non-symmetric collective states are commonly known as dark states of the cavity, akin to states without oscillator strength that emerge in molecular aggregates and molecular crystals [117, 129, 130]....

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References
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Journal ArticleDOI
TL;DR: In this article, an upper theoretical limit for the efficiency of p−n junction solar energy converters, called the detailed balance limit of efficiency, has been calculated for an ideal case in which the only recombination mechanism of holeelectron pairs is radiative as required by the principle of detailed balance.
Abstract: In order to find an upper theoretical limit for the efficiency of p‐n junction solar energy converters, a limiting efficiency, called the detailed balance limit of efficiency, has been calculated for an ideal case in which the only recombination mechanism of hole‐electron pairs is radiative as required by the principle of detailed balance. The efficiency is also calculated for the case in which radiative recombination is only a fixed fraction fc of the total recombination, the rest being nonradiative. Efficiencies at the matched loads have been calculated with band gap and fc as parameters, the sun and cell being assumed to be blackbodies with temperatures of 6000°K and 300°K, respectively. The maximum efficiency is found to be 30% for an energy gap of 1.1 ev and fc = 1. Actual junctions do not obey the predicted current‐voltage relationship, and reasons for the difference and its relevance to efficiency are discussed.

11,071 citations

Journal ArticleDOI
R. H. Dicke1
TL;DR: In this article, the authors considered a radiating gas as a single quantum-mechanical system, and the energy levels corresponding to certain correlations between individual molecules were described, where spontaneous emission of radiation in a transition between two such levels leads to the emission of coherent radiation.
Abstract: By considering a radiating gas as a single quantum-mechanical system, energy levels corresponding to certain correlations between individual molecules are described. Spontaneous emission of radiation in a transition between two such levels leads to the emission of coherent radiation. The discussion is limited first to a gas of dimension small compared with a wavelength. Spontaneous radiation rates and natural line breadths are calculated. For a gas of large extent the effect of photon recoil momentum on coherence is calculated. The effect of a radiation pulse in exciting "super-radiant" states is discussed. The angular correlation between successive photons spontaneously emitted by a gas initially in thermal equilibrium is calculated.

5,672 citations

Journal ArticleDOI
TL;DR: In this article, the authors present new insight into conduction mechanisms and performance characteristics, as well as opportunities for modeling properties of organic thin-film transistors (OTFTs) and discuss progress in the growing field of n-type OTFTs.
Abstract: Organic thin-film transistors (OTFTs) have lived to see great improvements in recent years. This review presents new insight into conduction mechanisms and performance characteristics, as well as opportunities for modeling properties of OTFTs. The shifted focus in research from novel chemical structures to fabrication technologies that optimize morphology and structural order is underscored by chapters on vacuum-deposited and solution-processed organic semiconducting films. Finally, progress in the growing field of the n-type OTFTs is discussed in ample detail. The Figure, showing a pentacene film edge on SiO2, illustrates the morphology issue.

4,804 citations

Journal ArticleDOI
TL;DR: Electronic Coupling in Oligoacene Derivatives: Factors Influencing Charge Mobility, and the Energy-Splitting-in-Dimer Method 3.1.
Abstract: 2.2. Materials 929 2.3. Factors Influencing Charge Mobility 931 2.3.1. Molecular Packing 931 2.3.2. Disorder 932 2.3.3. Temperature 933 2.3.4. Electric Field 934 2.3.5. Impurities 934 2.3.6. Pressure 934 2.3.7. Charge-Carrier Density 934 2.3.8. Size/molecular Weight 935 3. The Charge-Transport Parameters 935 3.1. Electronic Coupling 936 3.1.1. The Energy-Splitting-in-Dimer Method 936 3.1.2. The Orthogonality Issue 937 3.1.3. Impact of the Site Energy 937 3.1.4. Electronic Coupling in Oligoacene Derivatives 938

3,635 citations