Orientation Of Transition Dipole Moment Research Articles

Determining Excited-State Absorption Properties of a Quinoid Flavin by Polarization-Resolved Transient Spectroscopy.

As important naturally occurring chromophores, photophysical/chemical properties of quinoid flavins have been extensively studied both experimentally and theoretically. However, little is known about the transition dipole moment (TDM) orientation of excited-state absorption transitions of these important compounds. This aspect is of high interest in the fields of photocatalysis and quantum control studies. In this work, we employ polarization-associated spectra (PAS) to study the excited-state absorption transitions and the underlying TDM directions of a standard quinoid flavin compound. As compared to transient absorption anisotropy (TAA), an analysis based on PAS not only avoids diverging signals but also retrieves the relative angle for ESA transitions with respect to known TDM directions. Quantum chemical calculations of excited-state properties lead to good agreement with TA signals measured in magic angle configuration. Only when comparing experiment and theory for TAA spectra and PAS, do we find deviations when and only when the S0 → S1 of flavin is used as a reference. We attribute this to the vibronic coupling of this transition to a dark state. This effect is only observed in the employed polarization-controlled spectroscopy and would have gone unnoticed in conventional TA.

Shape-Dependent Optical Waveguides and Low-Threshold Lasers from Polymorphic Two-Dimensional Organic Single Crystals.

Organic single crystals (OSCs) with uniform morphologies and highly ordered molecular aggregations are promising for high-performance optoelectronic devices, such as organic solid-state lasers (OSSLs), organic light-emitting transistors (OLETs), and organic light-emitting diodes (OLEDs). However, manipulating OSC morphologies and aggregation is challenging. In this study, we synthesized two-dimensional (2D) OSCs of 4,4'-bis[(N-carbazole)styryl]biphenyl (BSBCz) in hexagonal and parallelogram microplate (H-MP and P-MP) forms. Both types exhibit H-aggregation in the 2D plate plane but with different molecular transition dipole moment (TDM) orientations. This leads to different photon coupling modes with H-MP and P-MP microcavities. H-MPs enable isotropic 2D-waveguiding, forming whispering gallery mode (WGM) resonators, while P-MPs create unidirectional waveguiding, forming Fabry-Pérot mode (FP) resonators. These resonators can generate low-threshold laser emissions at 467 and 473 nm, respectively, and exhibit superior lasing stability with a half-life exceeding 2 h. Our BSBCz microplate OSCs are attractive candidates to combine controlled organic microcavities with photon transporting for realizing future integrated optoelectronic devices.

Elucidating The Horizontal Orientation Mechanism of Emissive Transition Dipole Moment in A Series of Stick‐Like Delayed Fluorescent Emitters for Ultra‐High‐Efficiency OLEDs

AbstractThe horizontal orientation of the emissive transition dipole moment (TDM) of emissive molecules is a crucial factor in improving the efficiency of organic light‐emitting diodes (OLEDs). However, the mechanism of this horizontal orientation remains unclear. Herein, to elucidate the horizontal orientation mechanism of the TDM of the molecules in thermally activated delayed fluorescent (TADF) emitters, the relationship between the horizontal orientation ratio (Θ) of the TDM and the key parameters of stick‐like TADF emitters dispersed in carbazole‐based host materials is systematically and quantitatively investigated. The introduction of functional groups containing weak CH/n (n = O, N) hydrogen bonds into the host material is found to significantly increase the Θ values up to 30%. The physical parameters of the dispersed emitter exhibit a strong relationship with the Θ values, with the following influence order: glass transition temperature (Tg) ≥ total surface area of the largest π‐plane and the corresponding parallel π‐plane > molecular weight > aspect ratio > permanent dipole moment. The Tg value of the host material is another key parameter determining the Θ values. By using a P=O‐based host material, namely mCP2PO, a high PLQY of 97%, a high Θ value of 88%, and a sky‐blue OLED with an EQE of 37.6% are simultaneously realized.

Multimode vibrational dynamics and orientational effects in fluorescence-encoded infrared spectroscopy. I. Response function theory.

Fluorescence-encoded infrared (FEIR) spectroscopy is an emerging technique for performing vibrational spectroscopy in solution with detection sensitivity down to single molecules. FEIR experiments use ultrashort pulses to excite a fluorescent molecule's vibrational and electronic transitions in a sequential, time-resolved manner, and are therefore sensitive to intervening vibrational dynamics on the ground state, vibronic coupling, and the relative orientation of vibrational and electronic transition dipole moments. This series of papers presents a theoretical treatment of FEIR spectroscopy that describes these phenomena and examines their manifestation in experimental data. This first paper develops a nonlinear response function description of Fourier-transform FEIR experiments for a two-level electronic system coupled to multiple vibrations, which is then applied to interpret experimental measurements in the second paper [L. Whaley-Mayda et al., J. Chem. Phys. 159, 194202 (2023)]. Vibrational coherence between pairs of modes produce oscillatory features that interfere with the vibrations' population response in a manner dependent on the relative signs of their respective Franck-Condon wavefunction overlaps, leading to time-dependent distortions in FEIR spectra. The orientational response of population and coherence contributions are analyzed and the ability of polarization-dependent experiments to extract relative transition dipole angles is discussed. Overall, this work presents a framework for understanding the full spectroscopic information content of FEIR measurements to aid data interpretation and inform optimal experimental design.

Identifying the Quantitative Relationship Between the Molecular Structure and the Horizontal Transition Dipole Orientation of TADF Emitters

AbstractRealizing the horizontal orientation of molecular transition dipole moment (TDM) can greatly improve the out‐coupling efficiency and the resultant external quantum efficiency (EQE) of organic light‐emitting diodes (OLEDs). Herein, key parameters governing the horizontal TDM have been continuously explored. However, quantitatively identifying the key parameters from the molecular structure viewpoint is rather challenging due to the complexity of the influencing parameters. Here, by training the machine learning (ML) models using the experimental results, the quantitative relationship between the molecular structure and the horizontal TDM ratio (ϴ) of thermally activated delayed fluorescent (TADF) emitters in the host‐guest films is identified. The molecular structure is represented by either quantum chemistry‐calculated structural descriptors or topological/physical/chemical molecular descriptors. Key descriptors are ranked and can be used for guiding molecular structure design. Moreover, the accuracy of ML models is double‐verified by comparing the predicted results with experimental ϴ values and the trend of experimental EQE based on a group of materials. Using compressed sensing technology, the low‐dimension material space is also visually constructed based on key descriptors, and the results are consistent with those of the ML models.

Optimal subradiant spin wave exchange in dipole-coupled atomic ring arrays

The subwavelength array of quantum emitters provides an ideal platform for exploring rich many-body dynamics, such as super- and subradiance. In this paper, we explore the dynamics of spin wave exchange between two dipole-coupled atomic ring arrays. Subradiant spin waves lead to low-loss and high efficiency of ring-to-ring transfer. The optimal subradiant spin wave exchange occurs at appropriate separations between coplanar rings, despite the fact that the energy transfer efficiency is monotonically enhanced (in the regime ) as the rings’ separation decreases. However, the spin wave will scatter due to the dephasing mechanism of close-by atom pairs, as the separation of two rings is too small. With the increase in the number of atoms on the ring, the subradiant shielding effect also strengthens, leading to a shorter distance for the transfer of spin waves. We investigate the rotation of one of the rings and find that the optimal spin wave exchange corresponds to the scenario where the line connecting the two nearest atoms of the two rings aligns with the center of the circle. Moreover, we study the influence of transition dipole moment orientations on the effective interaction between two atomic rings. We observe that there is a critical point where the effective interaction strength changes dramatically owing to the cooperative effect of the subwavelength atomic array. We believe that our results could be important for quantum information processing based on atomic arrays.

Highly efficient organic light emitting diodes fabricated by solution process with new hole transport materials cross-linked at 120 °C

This work presents a rational design strategy for the synthesis of three thermal cross-linkable polystyrene-based hole transport copolymers (PPPIC-co-PBCB, PPIC-co-PBCB, PBIC-co-PBCB) by a simple free radical polymerization of planar structured indenocarbazole (IC)-based monomers having extended conjugated length and thermal cross-linkable benzocyclobutene (BCB). The materials show an extremely low cross-linking temperature of 120 °C and outstanding hole mobility of 1.01⨯10−2 cm2V−1s−1 at 4.0⨯105 Vcm−1. This value is one of the highest mobilities reported for thermal cross-linked hole transport materials (x-HTMs) in the literature. The preferred horizontal orientation of transition dipole moment (TDM), which is hardly obtained in spin coated film, was successfully achieved, and used for charge transport analysis. Herein, we also confirmed that the cross-linking reaction in our x-HTMs did not have any negative effect on the mobility of the layer, a correct method for mobility calculation from the space-charge limited current (SCLC) model was suggested, and the extension of interface mixing was also estimated for the first time. Furthermore, solution-processed organic light-emitting diode (s-OLED) device employing PPPIC-co-PBCB as HTM shows ultra-efficient performance of 130.5 cdA−1 and 37.3 % external quantum efficiency. To the best of our knowledge, this result is also one of the best efficiencies for phosphorescent s-OLEDs reported. The synthetic strategy for the polymers is also very simple with the cross-linkable monomers attached to the polystyrene backbone.

Composition Dictates Molecular Orientation at the Heterointerfaces of Vapor-Deposited Glasses.

Physical vapor deposition (PVD) can prepare organic glasses with a preferred molecular orientation. The relationships between deposition conditions and orientation have been extensively investigated in the film bulk. The role of interfaces on the structure is less well understood and remains a key knowledge gap, as the interfacial region can govern glass stability and optoelectronic properties. Robust experimental characterization has remained elusive due to complexities in interrogating molecular organization in amorphous, organic materials. Polarized soft X-rays are sensitive to both the composition and the orientation of transition dipole moments in the film, making them uniquely suited to probe molecular orientation in amorphous soft matter. Here, we utilize polarized resonant soft X-ray reflectivity (P-RSoXR) to simultaneously depth profile the composition and molecular orientation of a bilayer prepared through the physical vapor deposition of 1,4-di-[4-(N,N-diphenyl)amino]styryl-benzene (DSA-Ph) on a film of aluminum-tris(8-hydroxyquinoline) (Alq3). The bulk orientation of the DSA-Ph layer is controlled by varying deposition conditions. Utilizing P-RSoXR to depth profile the films enables determination of both the bulk orientation of DSA-Ph and the orientation near the Alq3 interface. At the Alq3 surface, DSA-Ph always lies with its long axis parallel to the interface, before transitioning into the bulk orientation. This is likely due to the lower mobility and higher glass transition of Alq3, as the first several monolayers of DSA-Ph deposited on Alq3 appear to behave as a blend. We further show how orientation at the interface correlates with the bulk behavior of a codeposited glass of similar blend composition, demonstrating a straightforward approach to predicting molecular orientation at heterointerfaces. This work provides key insights into how molecules orient during vapor deposition and offers methods to predict this property, a critical step toward controlling interfacial behavior in soft matter.

Dipole Moments and Transition Dipole Moments Calculated by Pair-Density Functional Theory with State Interaction

We develop response-function algorithms for dipole moments and transition dipole moments for compressed multistate pair-density functional theory (CMS-PDFT). We use the method of undetermined Lagrange multipliers to derive analytical expressions and validate them using numerical differentiation. We test the accuracy of the magnitudes of predicted ground-state and excited-state dipole moments, the orientations of these dipole moments, and the orientation of transition dipole moments by comparison to experimental data. We show that CMS-PDFT has good accuracy for these quantities, and we also show that, unlike methods that neglect state interaction, CMS-PDFT yields correct behavior for the dipole moment curves in the vicinity of conical intersections. This work, therefore, opens the door to molecular dynamic simulations in strong electric fields, and we envision that CMS-PDFT can now be used to discover chemical reactions that can be controlled by an oriented external electric field upon photoexcitation of the reactants.

Two‐Dimensional Organic Crystals Enabling Anisotropic Photon Transport and Dual‐Color Orthogonally Polarized Laser

AbstractAnisotropic transport of polarized photons in organic 2D crystals provides a great opportunity to construct integrated photonic circuits. However, such study remains a critical challenge limited by the precise orientation of molecular transition dipole moment (TDM) and modification of the interaction between photons and molecular TDM. Herein, a stilbene derivative with strong solid‐state photoluminescence is designed and synthesized. The excellent anisotropic polarization‐dependent waveguide occurs in its parallelogram 2D crystal and further enables 463‐ and 493‐nm lasing emissions along the short and long axes of the crystal, respectively. Polarization measurements show that the two lasers with the different wavelengths have mutually orthogonal linear polarizations. These results provide a new strategy for designing orthogonally polarized lasers in single‐component 2D crystals, which may inspire further development of organic photonic devices with controllable polarization properties.

Dynamics of transition dipole moment orientation in representative fluorescent proteins.

Molecules of fluorescent proteins (FPs) exhibit distinct optical directionality. This optical directionality is characterized by transition dipole moments (TDMs), and their orientation with respect to the molecular structures. Although our recent observations of FP crystals allowed us to determine the mean TDM directions with respect to the framework of representative FP molecules, the dynamics of TDM orientations within FP molecules remain to be ascertained. Here we describe the results of our investigations of the dynamics of TDM directions in the fluorescent proteins eGFP, mTurquoise2 and mCherry, through time-resolved fluorescence polarization measurements and microsecond time scale all-atom molecular dynamics (MD) simulations. The investigated FPs exhibit initial fluorescence anisotropies (r0) consistent with significant differences in the orientation of the excitation and emission TDMs. However, based on MD data, we largely attribute this observation to rapid (sub-nanosecond) fluorophore motions within the FP molecular framework. Our results allow improved determinations of orientational distributions of FP molecules by polarization microscopy, as well as more accurate interpretations of fluorescence resonance energy transfer (FRET) observations.

Confinement-Tunable Transition Dipole Moment Orientation in Perovskite Nanoplatelet Solids and Binary Blends.

Tuning the transition dipole moment (TDM) orientation in low-dimensional semiconductors is of fundamental and practical interest, as it enables high-efficiency nanophotonics and light-emitting diodes. However, despite recent progress in nanomaterials physics and chemistry, material systems that allow continuous tuning of the TDM orientation remain rare. Here, combining k-space photoluminescence spectroscopy and multiscale modeling, we demonstrate that the TDM orientation in lead halide perovskite (LHP) nanoplatelet (NPL) solids is largely confinement-tunable through the NPL geometry that regulates the anisotropy of Bloch states, dielectric confinement, and exciton fine structure. We further quantified the role of uniaxial ordering during NPL assembly in modifying the macroscopic emission directionality of thin films, which is especially important in actual optoelectronic devices. Our theoretical framework successfully corroborates the previous prediction of exciton bright level order reversal with experimental evidence of a counterintuitive reduction of in-plane dipole ratio in ultrathin (one- and two-monolayer-thick) NPLs, even at room temperature. More interestingly, the NPLs retain their TDM orientation in binary blends irrespective of interparticle energy transfer, owing to the phase segregation and NPL-NPL decoupling, enabling the design of films whose fluorescence exhibits an intrinsic angle-dependent color gradient.

Efficient Anisotropic Polariton Lasing Using Molecular Conformation and Orientation in Organic Microcavities

AbstractOrganic exciton‐photon polariton lasers are promising candidates for the efficient generation of coherent light at room temperature. While their thresholds are now comparable with those of conventional organic photon lasers, tuning of molecular conformation and orientation as a means to control fundamental properties of their emission and thus further enhance performance remains largely unexplored. Here, a two‐fold reduction in the threshold of a microcavity polariton laser based on an active layer of poly(9,9‐dioctylfluorene) (PFO) is achieved when 15% β‐phase conformation is introduced. In addtion, taking advantage of the liquid crystalline properties of PFO, a thin photoalignment layer is used to induce nematic alignment of the polymer chains. The resulting transition dipole moment orientation increases the Rabi energy, bringing the system into the ultra‐strong coupling regime and facilitating anisotropic polariton lasing with an eight‐fold reduction in absorbed threshold, down to 1.14 pJ (0.36 µJ cm−2) for the direction parallel to the orientation, with no emission along the orthogonal direction. This represents the first demonstration of anisotropic polariton lasing in conjugated polymer microcavities and a lower threshold than current organic vertical cavity surface‐emitting photon and polariton lasers. Dipole orientation offers new opportunities for switchable, more efficient polaritonic devices, and observation of fundamental effects at low polariton numbers.

Study of the Experimental and Simulated Vibrational Spectra Together with Conformational Analysis of Thioether Cyanobiphenyl-Based Liquid Crystal Dimers.

Infrared spectroscopy (IR) and quantum chemistry calculations that are based on the density functional theory (DFT) have been used to study the structure and molecular interactions of the nematic and twist-bend phases of thioether-linked dimers. Infrared absorbance measurements were conducted in a polarized beam for a homogeneously aligned sample in order to obtain more details about the orientation of the vibrational transition dipole moments. The distributions to investigate the structure and conformation of the molecule dihedral angle were calculated. The calculated spectrum was compared with the experimental infrared spectra and as a result, detailed vibrational assignments are reported.

Selective, Anisotropic, or Consistent Polarized‐Photon Out‐Coupling of 2D Organic Microcrystals

Nano- and micromaterials with anisotropic photoluminescence and photon transport have widespread application prospects in quantum optics, optoelectronics, and displays. But the nature of the polarization information of the out-coupled light, with respect to that of the source luminescence, has never been explored in active optical waveguiding organic crystals. Herein, three different modes (selective, anisotropic, and consistent) of polarized-photon out-coupling are proposed and successfully implemented in a set of 2D organic microcrystals with highly linearly-polarized luminescence. It is found that the polarization direction and degree of the luminescence out-coupled through different waveguiding channels can either be essentially retained or distinctly changed with respect to those of the original luminescence, depending on the molecular arrangement and the orientation of transition dipole moments of the crystal. This work demonstrates the promising potential of 2D emissive microcrystals in multi-channel polarized photon transport

Selective, Anisotropic, or Consistent Polarized-Photon Out-Coupling of 2D Organic Microcrystals.

Nano- and micromaterials with anisotropic photoluminescence and photon transport have widespread application prospects in quantum optics, optoelectronics, and displays. But the nature of the polarization information of the out-coupled light, with respect to that of the source luminescence, has never been explored in active optical-waveguiding organic crystals. Herein, three different modes (selective, anisotropic, and consistent) of polarized-photon out-coupling are proposed and successfully implemented in a set of 2D organic microcrystals with highly linearly-polarized luminescence. It is found that the polarization direction and degree of the luminescence out-coupled through different waveguiding channels can either be essentially retained or distinctly changed with respect to those of the original luminescence, depending on the molecular arrangement and the orientation of transition dipole moments of the crystal. This work demonstrates the promising potential of 2D emissive microcrystals in multi-channel polarized photon transport.

(Digital Presentation) Monitoring and Controlling Tautomerization in Phthalocyanines, Porphyrines and Porphycenes By Optical Single-Molecule Imaging and Spectroscopy

Tautomerization is an intramolecular chemical reaction defined as structural interconversion of a molecule between two isomers separated by a low energy barrier. Tautomerization in free base phthalocyanines, porphyrins or porphycenes has fascinated and attracted chemists and physicists alike over the last decades for its fundamental importance in various chemical and biological systems and many applications in technology [1,2]. Particularly interesting is the reaction rate which can range over orders of magnitude depending on the temperature and the local environment. In solution, this reaction in porphycenes occurs usually in several picoseconds or even faster, as determined via anisotropy studies by ultrafast transient absorption spectroscopy [3] and in porphyrins at cryogenic temperatures it can last for hours or days as determined form the live time of narrow spectral holes photochemically burned in the inhomogeneously broadened absorption band with a narrow band laser [4]. However, a spectacular and unexpected observation has been made by optical single molecule imaging and spectroscopy [5]. Examining a large number of single molecules embedded at low concentration in various polymer matrices at room temperature has revealed unquestionably that the rate in these molecules can vary dramatically over time such that tautomerization can be frozen for seconds and longer under ambient conditions[6]. The interconversion of the inner protons of phthalocyanine changes the orientation of the transition dipole moment by 90o degrees with respect to the molecular structure. Hence, if these molecules are embedded with a fixed orientation in a transparent solid polymer film at high dilution and tautomerization is frozen, the orientation of their transition dipole moments can be determined by polarization spectroscopy.Here we report on our recent experimental and theoretical studies of monitoring tautomerization by fluorescence imaging of single molecules of phthalocyanines, porphyrins, or porphycenes excited in the tightly focused azimuthally and radially polarized laser beam with a sample scanning confocal optical microscope equipped with single photon counting electronics and a fluorescence spectrometer. This technique has been used to determine the transition dipole moment orientation of single molecules, the polarizability of plasmonic nanoparticles or the dimensionality of single quantum dots. Different diffraction limited fluorescence intensity patterns are observed for molecules that undergo tautomerization and for those that do not. The latter corresponds to a molecule with a fixed transition dipole moment direction, whereas the tautomerizing molecule can be treated as the superposition of two emitters with different transition dipole moment orientations.Previous studies have shown that tautomerization in porphyrins or phthalocyanines can occur via ground state tunneling and is frozen at low temperatures, particularly at cryogenic temperatures. The structural heterogeneity in a polymer matrix leads to a distribution of asymmetrically distorted ground state double well potential and hence can lead to long residence times in the deeper energy minimum. However, even at helium temperatures tautomerization can be induced by electronic excitation to the first excited state, making photochemical spectral hole-burning possible. Recently we could demonstrate in a single-molecule study that the tautomerization rate of phthalocyanine tetrasulfonate embedded in a thin PVA-film at room temperature could be controlled in a tunable λ/2 Fabry Perot resonator by weak coupling between the electronically excited state and the vacuum electromagnetic field of a resonant cavity mode.

Magnetophotoselection in the Investigation of Excitonically Coupled Chromophores: The Case of the Water-Soluble Chlorophyll Protein.

A magnetophotoselection (MPS) investigation of the photoexcited triplet state of chlorophyll a both in a frozen organic solvent and in a protein environment, provided by the water-soluble chlorophyll protein (WSCP) of Lepidium virginicum, is reported. The MPS experiment combines the photoselection achieved by exciting with linearly polarized light with the magnetic selection of electron paramagnetic resonance (EPR) spectroscopy, allowing the determination of the relative orientation of the optical transition dipole moment and the zero-field splitting tensor axes in both environments. We demonstrate the robustness of the proposed methodology for a quantitative description of the excitonic interactions among pigments. The orientation of the optical transition dipole moments determined by the EPR analysis in WSCP, identified as an appropriate model system, are in excellent agreement with those calculated in the point-dipole approximation. In addition, MPS provides information on the electronic properties of the triplet state, localized on a single chlorophyll a pigment of the protein cluster, in terms of orientation of the zero-field splitting tensor axes in the molecular frame.

Anisotropic nanocrystal superlattices overcoming intrinsic light outcoupling efficiency limit in perovskite quantum dot light-emitting diodes

Quantum dot (QD) light-emitting diodes (LEDs) are emerging as one of the most promising candidates for next-generation displays. However, their intrinsic light outcoupling efficiency remains considerably lower than the organic counterpart, because it is not yet possible to control the transition-dipole-moment (TDM) orientation in QD solids at device level. Here, using the colloidal lead halide perovskite anisotropic nanocrystals (ANCs) as a model system, we report a directed self-assembly approach to form the anisotropic nanocrystal superlattices (ANSLs). Emission polarization in individual ANCs rescales the radiation from horizontal and vertical transition dipoles, effectively resulting in preferentially horizontal TDM orientation. Based on the emissive thin films comprised of ANSLs, we demonstrate an enhanced ratio of horizontal dipole up to 0.75, enhancing the theoretical light outcoupling efficiency of greater than 30%. Our optimized single-junction QD LEDs showed peak external quantum efficiency of up to 24.96%, comparable to state-of-the-art organic LEDs.

Dynamics of transition dipole orientation in representative fluorescent proteins

Molecules of fluorescent proteins behave like antennas: they exhibit distinct directionality of light absorption and emission. In our previous work we determined the mean orientations of the ‘molecular antennas’ (transition dipole moments) within the atomic framework of fluorescent protein molecules. In the presented work we use molecular dynamics simulations, as well as time resolved fluorescence anisotropy measurements, in order to investigate the dynamics of transition dipole moment orientation in representative fluorescent proteins.