Exciton Splitting Research Articles

Morphology-Controlled Organic Solar Cells Improved by a Nanohybrid System of Single Wall Carbon Nanotubes Sensitized by PbS Core/Perovskite Epitaxial Ligand Shell Quantum Dots

In the present work, a new solution processed nanohybrid system comprising of single-wall carbon nanotubes (SWCNTs) loaded by PbS quantum dots (QD) capped with an epitaxial ligand shell of methylammonium lead iodide perovskite clusters (MA4PbI6) is designed and fabricated. Attachment of PbS/PbI6 QDs on the surface of SWCNT is followed and evidenced by performing Fourier Transform Infrared Spectroscopy, X-ray photoelectron spectroscopy, and Field Emission Scanning Electron Microscopy. The steady state and dynamic photoluminescence results reveal efficient charge transfer from photo-excited PbS/PbI6 to SWCNTs. Very low amount (0.3 wt.%) of the as-synthesized PbS/PbI6-SWCNT is further incorporated into a polymeric solar cell containing P3HT and PC61BM and exhibits a power conversion efficiency improvement of around 15% compared to the P3HT:PC61BM bulk heterojunction reference solar cell. Significantly, loading perovskite capped PbS QDs on the surface of SWCNT works more efficient rather than incorporating PbS/PbI6 or SWCNT separately onto the composition of the photoactive layer. While PbS/PbI6 broaden the absorption window of photoactive layer and enhance the photon harvesting, their loading on the SWCNT has a significant influence on the faster exciton splitting by efficient electron transfer as well as keeping the desired crystallinity and nanoscale morphology of host matrix upon addition of QDs.

Charge Generation and Mobility-Limited Performance of Bulk Heterojunction Solar Cells with a Higher Adduct Fullerene

Alternative electron acceptors are being actively explored in order to advance the development of bulk-heterojunction (BHJ) organic solar cells (OSCs). The indene–C60 bisadduct (ICBA) has been regarded as a promising candidate, as it provides high open-circuit voltage in BHJ solar cells; however, the photovoltaic performance of such ICBA-based devices is often inferior when compared to cells with the omnipresent PCBM electron acceptor. Here, by pairing the high performance polymer (FTAZ) as the donor with either PCBM or ICBA as the acceptor, we explore the physical mechanism behind the reduced performance of the ICBA-based device. Time delayed collection field (TDCF) experiments reveal reduced, yet field-independent free charge generation in the FTAZ:ICBA system, explaining the overall lower photocurrent in its cells. Through the analysis of the photoluminescence, photogeneration, and electroluminescence, we find that the lower generation efficiency is neither caused by inefficient exciton splitting, nor ...

Structural and functional investigation of allophycocyanin trimer

Nature has been developing and optimizing photosynthesis billions years, including green plants, algae, photosynthetic bacteria and cyanobacteria. Phycobiliproteins system, as the phycobilisomes, in cyanobacteria and red algae is the one of two major light-harvesting systems, after evolution in billions years. Allophycocyanin (APC) trimer is a primary composition of phycobilisomes core for efficient lower-energy photons funneling pathway. In 2009, Liu et al. have firstly assembled the highly soluble self-assembled recombinant APC trimer with N-terminus polyhistidine, which the entire biosynthesis pathway of APC trimer was reconstituted in Escherichia coli strain with the full-length genes of apoprotein α subunit and β subunit from Synechocystis sp. PCC 6803. The recombinant APC trimer was used to be the subject in this research. An optimum protocol with immobilized metal-ion affinity chromatography with chelating transition metal ion (Ni2+) was used to purify the recombinant protein. Then, the second purification was performed to obtain APC trimer with a higher purity ( A 650/ A 620=1.346), using density gradient centrifugation. Single molecules of recombinant APC trimers were investigated with atomic force microscopy. Three-dimensional images with resolution at nanoscale indicated that the recombinant allophycocyanin trimers were approximately 1.5 nm in short axis, and 15 nm in long axis, which were in accordance with the sizes of natural allophycocyanin trimer measured by transmission electron microscopy or X-ray crystallography. Moreover, the correct conformation of recombinant allophycocyanin trimer was confirmed by fluorescence spectra (studied energy transfer ability), absorption spectra (studied the light-harvesting ability), and circular dichroism (CD) spectra (studied changes of secondary structure and aggregation state). The CD spectra of recombinant allophycocyanin induced by a wide range of pH were analyzed both at wavelengths in ultraviolet range (190–250 nm) and visible range (450–750 nm). The α -helices were the dominant secondary structure in recombinant allophycocyanin trimer by analysis of CD spectra in ultraviolet range, while the analysis of CD spectra in visible range suggested the existence of exciton-coupled pairs of phycocyanobilins, in which the energy transfer was mainly in the form of exciton splitting. By studying its spectra property variations in response to pH changes, we found that recombinant APC trimer showed good absorbance and fluorescence stability at varying pH. The conformation of chromophores in recombinant APC trimer was relatively stable, between the range of pH 4–9, which was revealed by the stable absorption and fluorescence spectra properties of recombinant APC trimer. The trimeric structure of recombinant APC was maintained while local variations of protein peptides were also shown in response to the environmental disturbance. Beyond this pH range, secondary structure as well as overall conformation of recombinant APC dramatically changed, and the energy absorption and transfer ability were also disrupted. This work demonstrated that correct function in energy transfer was retained in the recombinant allophycocyanin trimer compared with nature allophycocyanin trimer.

Even exciton series in Cu2O

In $\mathrm{Cu_{2}O}$ parity is a good quantum number and thus the exciton spectrum falls into two parts: The dipole-active exciton states of negative parity and odd angular momentum, which can be observed in one-photon absorption ($\Gamma_4^-$ symmetry) and the exciton states of positive parity and even angular momentum, which can be observed in two-photon absorption ($\Gamma_5^+$ symmetry). The unexpected observation of $D$ excitons in two-photon absorption and of $F$ excitons in one-photon absorption has given evidence that the dispersion properties of the $\Gamma_5^+$ orbital valence band is giving rise to a coupling of the yellow and green exciton series. In this paper we show that the even and odd parity exciton system can be consistently described within the same theoretical approach. However, the Hamiltonian of the even parity system needs, in comparison to the odd exciton case, modifications to account for the very small radius of the $1S$ exciton. In the presented treatment we take special care of the central-cell corrections, which comprise a reduced screening of the Coulomb potential at distances comparable to the polaron radius, the exchange interaction being responsible for the exciton splitting into ortho and para states, and the inclusion of terms in the fourth power of $p$ in the kinetic energy. Since the yellow $1S$ exciton state is coupled to all other states of positive parity, we show how the central-cell corrections affect the whole even exciton series. The close resonance of the $1S$ green exciton with states of the yellow exciton series has a strong impact on the energies and oscillator strengths of all implied states. The consistency between theory and experiment with respect to energies and oscillator strengths for the even and odd exciton system in $\mathrm{Cu_{2}O}$ is a convincing proof for the validity of the applied theory.

Spatially resolved extrinsic photoresponse under additional intrinsic bias photoexcitation of two terminal pentacene devices

Spatially resolved extrinsic photoresponse experiments in pentacene two terminal devices without or under additional intrinsic bias-light excitation are employed. These experiments are used to investigate the microscopic mechanism of the recently observed phenomenon of the photoresponse enhancement under additional bias-light intrinsic excitation and to preclude that this phenomenon arises from contact-related artifacts. It is found that the extrinsic photogeneration near the contacts via electric field-assisted exciton splitting and/or light-induced depletion width-reduction have a negligible contribution to the extrinsic photoresponse. Under additional bias-light intrinsic excitation, a uniform increase of the photogenerated hole density is found to take place across the whole conduction channel, without changes in the electric field distribution and in the interfacial properties of the contacts. The photoresponse enhancement by the blue bias-light becomes stronger upon increasing the red-light intensity. A nearly square root dependence of the photoresponse enhancement on the blue bias-light intensity is found. It is shown that the observed dependence of the photoresponse enhancement on the light intensities of the extrinsic and intrinsic excitation can be explained with the extrinsic photogeneration mechanism based on hole detrapping by triplet exciton dissociation.

Atomistic theory of excitonic fine structure in InAs/InP nanowire quantum dot molecules

Nanowire quantum dots have peculiar electronic and optical properties. In this work we use atomistic tight binding to study excitonic spectra of artificial molecules formed by a double nanowire quantum dot. We demonstrate a key role of atomistic symmetry and nanowire substrate orientation rather than cylindrical shape symmetry of a nanowire and a molecule. In particular for $[001]$ nanowire orientation we observe a nonvanishing bright exciton splitting for a quasimolecule formed by two cylindrical quantum dots of different heights. This effect is due to interdot coupling that effectively reduces the overall symmetry, whereas single uncoupled $[001]$ quantum dots have zero fine structure splitting. We found that the same double quantum dot system grown on $[111]$ nanowire reveals no excitonic fine structure for all considered quantum dot distances and individual quantum dot heights. Further we demonstrate a pronounced, by several orders of magnitude, increase of the dark exciton optical activity in a quantum dot molecule as compared to a single quantum dot. For $[111]$ systems we also show spontaneous localization of single particle states in one of nominally identical quantum dots forming a molecule, which is mediated by strain and origins from the lack of the vertical inversion symmetry in $[111]$ nanostructures of overall ${C}_{3v}$ symmetry. Finally, we study lowering of symmetry due to alloy randomness that triggers nonzero excitonic fine structure and the dark exciton optical activity in realistic nanowire quantum dot molecules of intermixed composition.

1,3-Bis(thieno[3,4-b]thiophen-6-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione-Based Small-Molecule Donor for Efficient Solution-Processed Solar Cells.

A small molecule TBTT-1 with 5-(2-ethylhexyl)-1,3-bis(2-(2-ethylhexyl)thieno[3,4-b]thiophen-6-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (TBTT) as the central moiety was designed and synthesized for solution-processed bulk-heterojunction solar cells. TBTT-1 exhibits a broad absorption with a low optical band gap of approximately 1.53 eV in the thin film. An optimized power conversion efficiency (PCE) of 7.47% with a high short-circuit current of 14.95 mA cm-2 was achieved with diphenyl ether (DPE) as additive, which is the highest PCE for TPD-based small-molecule solar cells. According to the detailed morphology investigations, we found that DPE processing helped to enhance π-π stacking and reduce the scales of phase separation, which led to improved exciton splitting and charge transport in BHJ thin film, and thus enhanced device performance.

Geometric and Electronic Structures of Dibenzo-15-Crown-5 Complexes with Alkali Metal Ions Studied by UV Photodissociation and UV-UV Hole-Burning Spectroscopy.

We measure UV photodissociation (UVPD) and UV-UV hole-burning (HB) spectra of dibenzo-15-crown-5 (DB15C5) complexes with alkali metal ions, M+·DB15C5 (M = Li, Na, K, Rb, and Cs), under cold (∼10 K) conditions in the gas phase. The UV-UV HB spectra of the M+·DB15C5 (M = K, Rb, and Cs) complexes indicate that there is one dominant conformation for each complex except the Na+·DB15C5 complex, which has two conformers with a comparable abundance ratio. It was previously reported that the M+·(benzo-15-crown-5) (M+·B15C5, M = K, Rb, and Cs) complexes each have three conformers. Thus, the attachment of one additional benzene ring to the crown cavity of benzo-15-crown-5 reduces conformational flexibility, giving one dominant conformation for the M+·DB15C5 (M = K, Rb, and Cs) complexes. In the UVPD spectra of the K+·DB15C5, Rb+·DB15C5, and Cs+·DB15C5 complexes, the S1-S0 and S2-S0 transitions are observed independently at different positions with different vibronic structures. The spectral features are substantially different from those of the K+·(dibenzo-18-crown-6) (K+·DB18C6) complex, which belongs to the C2v point group and exhibits exciton splitting with an interval of 2.7 cm-1. The experimental and theoretical results suggest that in the M+·DB15C5 complexes the two benzene rings are not symmetrically equivalent with each other and the S1-S0 and S2-S0 electronic excitations are almost localized in one of the benzene rings. The electronic interaction energy between the two benzene chromophores is compared between the K+·DB15C5 and K+·DB18C6 complexes by quantum chemical calculations. The interaction energy of the K+·DB15C5 complex is estimated to be less than half of that of the K+·DB18C6 complex (∼30 cm-1) due to less suitable relative angles between the transition dipole moments of the two benzene chromophores in K+·DB15C5.

Polarization-Dependent Interference of Coherent Scattering from Orthogonal Dipole Moments of a Resonantly Excited Quantum Dot.

Resonant photoluminescence excitation (RPLE) spectra of a neutral InGaAs quantum dot show unconventional line shapes that depend on the detection polarization. We characterize this phenomenon by performing polarization-dependent RPLE measurements and simulating the measured spectra with a three-level quantum model. The spectra are explained by interference between fields coherently scattered from the two fine structure split exciton states, and the measurements enable extraction of the steady-state coherence between the two exciton states.

Brightening of dark excitons in monolayers of semiconducting transition metal dichalcogenides

We present low-temperature magneto-photoluminescence experiments which demonstrate the brightening of dark excitons by an in-plane magnetic field B applied to monolayers of different semiconducting transition metal dichalcogenides. For WSe2 and WS2 monolayers, the dark exciton emission is observed at ∼50 meV below the bright exciton peak and displays a characteristic doublet structure whose intensity grows with B2, while no magnetic field induced emission peaks appear for MoSe2 monolayer. Our experiments also show that the MoS2 monolayer has a dark exciton ground state with a dark-bright exciton splitting energy of ∼100 meV.

Long-lived magnetoexcitons in 2D-fermion system

The paper addresses the experimental technique that, when applied to a 2D-electron system in the integer quantum Hall regime with filling factor ν = 2 (the Hall insulating state), allows resonant excitation of magnetoexcitons, their detection, control of an ensemble of long-lived triplet excitons and investigation of their radiationless decay related to exciton spin relaxation into the ground state. The technique proposed enables independent control of photoexcited electrons and Fermi-holes using photoinduced resonance reflection spectra as well as estimate with a reasonable degree of accuracy the resulting density of photoinduced electron-hole pairs bound into magnetoexcitons. The mere existence of triplet excitons was directly established by inelastic light scattering spectra which were analyzed to determine the value of singlet-triplet exciton splitting. It was found that the lifetimes of triplet excitons conditioned by electron spin relaxation in highly perfect GaAs/AlGaAs heterostructures with highly mobile 2D electrons are extremely long exceeding 100 μs at T < 1 K. The paper presents a qualitative explanation of the long-spin relaxation lifetimes which are unprecedented for translation-invariant 2D systems. This enabled us to create sufficiently high concentrations of triplet magnetoexcitons, electrically neutral excitations following Bose–Einstein statistics, in a Fermi electron system and investigate their collective properties. At sufficiently high densities of triplet magnetoexcitons and low temperatures, T < 1 K, the degenerate magnetofermionic system exhibits condensation of the triplet magnetoexcitons into a qualitatively new collective state with unusual properties which occurs in the space of generalized moments (magnetic translation vectors). The occurrence of a condensed phase is accompanied with a significant decrease in the viscosity of the photoexcited system, which is responsible for electron spin transport at macroscopic distances, as well as with the effects of threshold enhancement of the system response to the external action of the electromagnetic field and emergence of a new intensive radiative recombination channel.

Excitonic Splitting and Vibronic Coupling Analysis of the m-Cyanophenol Dimer.

The S1/S2 splitting of the m-cyanophenol dimer, (mCP)2 and the delocalization of its excitonically coupled S1/S2 states are investigated by mass-selective two-color resonant two-photon ionization and dispersed fluorescence spectroscopy, complemented by a theoretical vibronic coupling analysis based on correlated ab initio calculations at the approximate coupled cluster CC2 and SCS-CC2 levels. The calculations predict three close-lying ground-state minima of (mCP)2: The lowest is slightly Z-shaped (Ci-symmetric); the second-lowest is <5 cm-1 higher and planar (C2h). The vibrational ground state is probably delocalized over both minima. The S0 → S1 transition of (mCP)2 is electric-dipole allowed (Ag → Au), while the S0 → S2 transition is forbidden (Ag → Ag). Breaking the inversion symmetry by 12C/13C- or H/D-substitution renders the S0 → S2 transition partially allowed; the excitonic contribution to the S1/S2 splitting is Δexc = 7.3 cm-1. Additional isotope-dependent contributions arise from the changes of the m-cyanophenol zero-point vibrational energy upon electronic excitation, which are Δiso(12C/13C) = 3.3 cm-1 and Δiso(H/D) = 6.8 cm-1. Only partial localization of the exciton occurs in the 12C/13C and H/D substituted heterodimers. The SCS-CC2 calculated excitonic splitting is Δel = 179 cm-1; when multiplying this with the vibronic quenching factor Γvibronexp = 0.043, we obtain an exciton splitting Δvibronexp = 7.7 cm-1, which agrees very well with the experimental Δexc = 7.3 cm-1. The semiclassical exciton hopping times range from 3.2 ps in (mCP)2 to 5.7 ps in the heterodimer (mCP-h)·(mCP-d). A multimode vibronic coupling analysis is performed encompassing all the vibronic levels of the coupled S1/S2 states from the v = 0 level to 600 cm-1 above. Both linear and quadratic vibronic coupling schemes were investigated to simulate the S0 → S1/S2 vibronic spectra; those calculated with the latter scheme agree better with experiment.

Stokes shift and fine structure splitting in composition-tunable ZnxCd1−xSe nanocrystals: Atomistic tight-binding theory

I report on the atomistic correlation of the structural properties and excitonic splitting of ternary alloy ZnxCd1−xSe wurtzite nanocrystals using the sp3s* empirical tight-binding method with the description of the first nearest neighbouring interaction and bowing effect. Based on a successful model, the computations are presented under various Zn compositions (x) and diameters of alloy ZnxCd1−xSe nanocrystals with the experimentally synthesized compositions and sizes. With increasing Zn contents (x), the optical band gaps and electron-hole coulomb energies are improved, while ground electron-hole wave function overlaps, electron-hole exchange energies, stokes shift and fine structure splitting are reduced. A composition-tunable emission from blue to yellow wavelength is obviously demonstrated. The optical band gaps, ground electron-hole wave function overlaps, electron-hole interactions, stokes shift and fine structure splitting are progressively decreased with the increasing diameters. Alloy ZnxCd1−xSe nanocrystal with Zn rich and large diameter is the best candidate to optimistically be used as a source of entangled photon pairs. The agreement with the experimental data is remarkable. Finally, the present systematic study on the structural properties and excitonic splitting predominantly opens a new perspective to understand the size- and composition-dependent properties of ZnxCd1−xSe nanocrystals with a comprehensive strategy to design the optoelectronic devices.

Atomistic tight-binding theory of excitonic splitting energies in CdX(X = Se, S and Te)/ZnS core/shell nanocrystals

Using the atomistic tight-binding theory (TB) and a configuration interaction description (CI), we numerically compute the excitonic splitting of CdX(X = Se, S and Te)/ZnS core/shell nanocrystals with the objective to explain how types of the core materials and growth shell thickness can provide the detailed manipulation of the dark-dark (DD), dark-bright (DB) and bright-bright (BB) excitonic splitting, beneficial for the active application of quantum information. To analyze the splitting of the excitonic states, the optical band gaps, ground-state wave function overlaps and atomistic electron-hole interactions tend to be numerically demonstrated. Based on the atomistic computations, the single-particle and excitonic gaps are mainly reduced with the increasing ZnS shell thickness owing to the quantum confinement. In the range of the higher to lower energies, the order of the single-particle gaps is CdSe/ZnS, CdS/ZnS and CdTe/ZnS core/shell nanocrystals, while one of the excitonic gaps is CdS/ZnS, CdSe/ZnS and CdTe/ZnS core/shell nanocrystals because of the atomistic electron-hole interaction. The strongest electron-hole interactions are mainly observed in CdSe/ZnS core/shell nanocrystals. In addition, the computational results underline that the energies of the dark-dark (DD), dark-bright (DB) and bright-bright (BB) excitonic splitting are generally reduced with the increasing ZnS growth shell thickness as described by the trend of the electron-hole exchange interaction. The high-to-low splitting of the excitonic states is demonstrated in CdSe/ZnS, CdTe/ZnS and CdS/ZnS core/shell nanocrystals because of the fashion in the electron-hole exchange interaction and overlaps of the electron-hole wave functions. As the resulting calculations, it is expected that CdS/ZnS core/shell nanocrystals are the best candidates to be the source of entangled photons. Finally, the comprehensive information on the excitonic splitting can enable the use of suitable core/shell nanocrystals for the entangled photons in the application of quantum information.

Optical absorption and transmission in a molybdenum disulfide monolayer

Our recently proposed theoretical formulation [presented in D. Novko et al., Phys. Rev. B 93, 125413 (2016)] is used to study optical absorption and transmission in molybdenum disulfide $({\mathrm{MoS}}_{2})$ monolayer as a function of incident photon energy and angle. The investigation is not focused on exploration of well-documented spin-orbit split excitons around optical absorption onset, but rather on the most intensive features in absorption spectrum in the visible and near-ultraviolet photon energy range $(1.7--4\phantom{\rule{0.28em}{0ex}}\mathrm{eV})$. It is shown that three most intensive peaks, at 2.7, 3.1, and 3.7 eV, result from transitions between $\text{Mo}(d)$ and $\text{S}(p)$ valence and conduction bands and that the character of their charge/current density fluctuations is intrinsically in plane, located in the molybdenum plane. This also implies that ${\mathrm{MoS}}_{2}$ monolayer is completely transparent when illuminated by grazing incidence $p$-polarized light. The validity of the presented results is supported by our effective two-band tight-binding model and finally by good agreement with some recent experimental results.

Triazolobenzothiadiazole‐Based Copolymers for Polymer Light‐Emitting Diodes: Pure Near‐Infrared Emission via Optimized Energy and Charge Transfer

A series of new near‐infrared (NIR) emitting copolymers, based on a low band gap 6‐(2‐butyloctyl)‐4,8‐di(thiophen‐2‐yl)‐[1,2,3]triazolo[4′,5′:4,5]benzo[1,2‐c]‐[1,2,5]thiadiazole (TBTTT) fluorophore copolymerized into a high band gap poly[3,3′‐ditetradecyl‐2,2′‐bithiophene‐5,5′‐diyl‐alt‐5‐(2‐ethylhexyl)‐4H‐thieno[3,4‐c]pyrrole‐4,6(5H)‐dione‐1,3‐diyl] (P2TTPD) host backbone, for polymer light‐emitting diode (PLED) applications is reported. PLEDs fabricated from the host polymer (P2TTPD‐0) show external quantum efficiencies (EQEs) up to 0.49% at 690 nm, with turn‐on voltage (Von) at only 2.4 V. By incorporating the TBTTT segments into the host polymer backbone, pure NIR emission peaking at ca. 900 nm is obtained with Von remaining below 5 V. This work demonstrates that such a low Von can be attributed to efficient intrachain energy and/or charge transfer to the TBTTT sites. When the NIR emitting copolymer (P2TTPD‐10) is blended with P2TTPD‐0, the TBTTT are confined to well‐separated polymer chains. As a result, the EQE from the blend is lower and the Von higher than that obtained from the pure copolymer (P2TTPD‐1.0) with equal content of TBTTT. An analogous copolymer (P4T‐1.0), consisting of poly[3,3′‐ditetradecyl‐2,2′:5′,2′′:5′′,2′′′‐quaterthiophene‐5,5′′′‐diyl] (P4T) as the host and 1% TBTTT as the NIR emitter, further demonstrates that pure NIR emission can be obtained only through optimized molecular orbital energy levels, as in P2TTPD‐1.0, which minimizes chances for either charge trapping or exciton splitting.

Coupling of Excitons and Discrete Acoustic Phonons in Vibrationally Isolated Quantum Emitters.

The photoluminescence emission by mesoscopic condensed matter is ultimately dictated by the fine-structure splitting of the fundamental exciton into optically allowed and dipole-forbidden states. In epitaxially grown semiconductor quantum dots, nonradiative equilibration between the fine-structure levels is mediated by bulk acoustic phonons, resulting in asymmetric spectral broadening of the excitonic luminescence. In isolated colloidal quantum dots, spatial confinement of the vibrational motion is expected to give rise to an interplay between the quantized electronic and phononic degrees of freedom. In most cases, however, zero-dimensional colloidal nanocrystals are strongly coupled to the substrate such that the charge relaxation processes are still effectively governed by the bulk properties. Here we show that encapsulation of single colloidal CdSe/CdS nanocrystals into individual organic polymer shells allows for systematic vibrational decoupling of the semiconductor nanospheres from the surroundings. In contrast to epitaxially grown quantum dots, simultaneous quantization of both electronic and vibrational degrees of freedom results in a series of strong and narrow acoustic phonon sidebands observed in the photoluminescence. Furthermore, an individual analysis of more than 200 compound particles reveals that enhancement or suppression of the radiative properties of the fundamental exciton is controlled by the interaction between fine-structure states via the discrete vibrational modes. For the first time, pronounced resonances in the scattering rate between the fine-structure states are directly observed, in good agreement with a quantum mechanical model. The unambiguous assignment of mediating acoustic modes to the observed scattering resonances complements the experimental findings. Thus, our results form an attractive basis for future studies on subterahertz quantum opto-mechanics and efficient laser cooling at the nanoscale.

Molecular pore-wall engineering of mesozeolitic conjugated polymers for photoredox hydrogen production with visible light

A chemical protocol based on molecular engineering of polymeric matrix is developed for the chemical optimization of ordered mesoporous carbon nitride (OMCN) in this study to address the concerns on the serious nanostructure-induced semiconductive defects, in particular the remarkable hypsochromic shift of absorption threshold and the increased excition dissociation energy. Physical characterizations demonstrate that the successful incorporation of 3-aminothiophene-2-carbonitrile (ATCN) aromatic donor in OMCN matrix can efficiently extend the π-conjugated system, red-shift the optical absorption toward longer wavelengths and promote exciton splitting, thus well overcoming the serious semiconductive defects. In addition, the unique structural benefits of OMCN, such as the well-orientated nanoarchitectures with large specific surface area and uniform nanosized pore, have been well remained in ATCN-modified sample (OMCNA) via adjusting the ATCN/cyanamide molar ratio to minimize the unavoidable matrix disturbance. Hence, an obviously enhanced photocatalytic activity toward H2 evolution and selective oxidation of alcohols are obtained on optimized OMCNA samples, greatly underlining the advantage of molecular engineering in supporting nanostructured photocatalysts.

Exploring the Light-Capturing Properties of Photosynthetic Chlorophyll Clusters Using Large-Scale Correlated Calculations.

Chlorophylls are light-capturing units found in photosynthetic proteins. We study here the ground and excited state properties of monomeric, dimeric, and tetrameric models of the special chlorophyll/bacteriochlorophyll (Chl/BChl) pigment (P) centers P700 and P680/P870 of type I and type II photosystems, respectively. In the excited state calculations, we study the performance of the algebraic diagrammatic construction through second-order (ADC(2)) method in combination with the reduced virtual space (RVS) approach and the recently developed Laplace-transformed scaled-opposite-spin (LT-SOS) algorithm, which allows us, for the first time, to address multimeric effects at correlated ab initio levels using large basis sets. At the LT-SOS-RVS-ADC(2)/def2-TZVP level, we obtain vertical excitation energies (VEEs) of 2.00-2.07 and 1.52-1.62 eV for the P680/P700 and the P870 pigment models, respectively, which agree well with the experimental absorption maxima of 1.82, 1.77, and 1.43 eV for P680, P700, and P870, respectively. In the P680/P870 models, we find that the photoexcitation leads to a π → π* transition in which the exciton is delocalized between the adjacent Chl/BChl molecules of the central pair, whereas the exciton is localized to a single chlorophyll molecule in the P700 model. Consistent with experiments, the calculated excitonic splittings between the central pairs of P680, P700, and P870 models are 80, 200, and 400 cm(-1), respectively. The calculations show that the electron affinity of the radical cation of the P680 model is 0.4 V larger than for the P870 model and 0.2 V larger than for P700. The chromophore stacking interaction is found to strongly influence the electron localization properties of the light-absorbing pigments, which may help to elucidate mechanistic details of the charge separation process in type I and type II photosystems.

Do Hydrogen Bonds Influence Excitonic Splittings?

The excitonic splitting and vibronic quenching of the inversion-symmetric homodimers of benzonitrile, (BN)2, and meta-cyanophenol, (mCP)2, are investigated by two-color resonant two-photon ionization spectroscopy. These systems have very different hydrogen bond strengths: the OH···N≡C bonds in (mCP)2 are ∼10 times stronger than the CH···N≡C hydrogen bonds in (BN)2. In (BN)2 the S0((1)Ag) → S1((1)Ag) transition is electric-dipole forbidden, while the S0((1)Ag) → S2((1)Bu) transition is allowed. The opposite holds for (mCP)2 due to the different transition dipole moment vector alignment. The S0 → S1S2 spectra of the dimers are compared and their excitonic splittings and vibronic quenchings are investigated by measuring the (13)C-substituted heterodimer isotopomers, for which the centrosymmetry is broken and both transitions are allowed. The excitonic splittings are determined as Δexc = 2.1 cm(-1) for (BN)2 and Δexc = 7.3 cm(-1) for (mCP)2. The latter exhibits a much stronger vibronic quenching, as the purely electronic splitting resulting from ab initio calculations is determined to be Δcalc = 179 cm-1, while in (BN)2 the calculated splitting is Δcalc = 10 cm(-1). The monomer site-shifts upon dimerization and comparing certain vibrations that deform the hydrogen bonds confirm that the OH···N≡C hydrogen bond is much stronger than the CH···N≡C bond. We show that the H-bonds have large effects on the spectral shifts, but little or no influence on the excitonic splitting.