Core molecule dependence of energy migration in phenylacetylene nanostar dendrimers: Ab initio molecular orbital-configuration interaction based quantum master equation study

The core molecule dependence of energy (exciton) migration in phenylacetylene nanostar dendrimers is investigated using the ab initio molecular orbital (MO)-configuration interaction based quantum master equation approach. We examine three kinds of core molecular species, i.e., benzene, anthracene, and pentacene, with different highest occupied MO-lowest unoccupied MO (HOMO-LUMO) gaps, which lead to different orbital interactions between the dendron parts and the core molecule. The nanostars bearing anthracene and pentacene cores are characterized by multistep exciton states with spatially well-segmented distributions: The exciton distributions of high-lying exciton states are spatially localized well in the periphery region, whereas those of low-lying exciton states are done in the core region. On the other hand, for the nanostar bearing benzene core, which also has multistep exciton states, the spatial exciton distributions of low-lying exciton states are delocalized over the dendron and the core regions. It is found that the former nanostars exhibit nearly complete exciton migration from the periphery to the core molecule in contrast to the latter one, in which significant exciton distribution remains in the dendron parts attached to the core after the exciton relaxation, although all these dendrimers exhibit fast exciton relaxation from the initially populated states. It is predicted from the analysis based on the MO correlation diagrams and the relative relaxation factor that the complete exciton migration to the core occurs not only when the HOMO-LUMO gap of the core molecule is nearly equal to that of the dendron parts attached to the core (anthracene case) but also when fairly smaller than that (pentacene case), whereas the complete migration is not achieved when the HOMO-LUMO gap of the core is larger than that of the dendron parts (benzene case). These results suggest that the fast and complete exciton migration of real dendrimers could be realized by adjusting the HOMO-LUMO gap of the core molecule to be smaller than that of dendron parts, although there exist more complicated relaxation processes as compared to simple dendritic aggregate models studied so far.     

Theoretical study on second hyperpolarizabilities of phenylacetylene dendrimer: toward an understanding of structure-property relation in NLO responses of fractal antenna dendrimers

This contribution explores the relation between molecular second hyperpolarizabilities (gamma) and molecular architecture in phenylacetylene dendrimers using the semiempirical molecular orbital method, that is, INDO/S method. The orientationally averaged gamma of a large-size phenylacetylene dendrimer, which is composed of 24 units of phenylacetylenes and is referred to as D25, is found to be about 50 times as large as that of the diphenylacetylene monomer. In contrast, the gamma(s)() value of D25 is found to be about 6 times as small as that of the para-substituted phenylacetylene oligomer (L25) composed of 24 units of phenylacetylenes. To investigate the structure-property relation in gamma for D25 and L25, we examine the spatial contributions of electrons to gamma values using gamma density analysis. The present analysis reveals that the dominant contributions of electrons to gamma of D25 are localized in the linear-leg regions parallel to the applied electric field and the contributions are also well segmented at the meta-connected points (benzene rings), while the spatial distribution of the gamma density of L25 is extended over the whole region of the chain, and the dominant contribution stems from the both-end regions. It is found for D25 that the magnitude of contributions to gamma in the internal region is more enhanced than that in the outer region. We further found that the magnitudes of contributions in internal linear-leg regions of D25 are somewhat larger than those of the same-size isolated linear-leg molecules. This suggests that the slightly remaining pi-conjugations via the meta-branching points still enhance the contributions to gamma localized in the linear-leg regions. These features of spatial contributions to gamma of D25 are found to originate in the fractal architecture, in which pi-conjugation lengths in the linear-leg region increase on going from the periphery to the core. Finally, fractal antenna dendrimers are expected to be promising novel nonlinear optical (NLO) substances with a controllability of the magnitude and spatial contribution of the third-order NLO properties.     

Quantum master equation approach to the second hyperpolarizability of nanostar dendritic systems

We investigate the dynamic second hyperpolarizability (gamma) of nanostar dendritic systems using the quantum master equation approach. In the nanostar dendritic systems composed of three-state monomers, the multistep exciton states are obtained by the dipole-dipole interactions, and the directional energy transport, i.e., exciton migration, from the periphery to the core is predicted to occur by the relaxation between exciton states originating in the exciton-phonon coupling. The effects of the intermolcecular interaction and the exciton migration, i.e., exciton relaxation, on the gamma in the third-harmonic generation (THG) are examined in the three-photon off- and on- resonance regions using the two-exciton model. Furthermore, the method for analysis of spatial contributions of excitons to gamma is presented by partitioning the total gamma into the one- and two-exciton contributions. It turns out that the exciton relaxation between exciton states causes significant broadening of the spectra of gamma and their mutual overlap as well as the relative increase of two-exciton contributions in the nanostar dendritic system.     

Low-temperature dynamics of weakly localized Frenkel excitons in disordered linear chains

We calculate the temperature dependence of the fluorescence Stokes shift and the fluorescence decay time in linear Frenkel exciton systems resulting from the thermal redistribution of exciton population over the band states. The following factors, relevant to common experimental conditions, are accounted for in our kinetic model: (weak) localization of the exciton states by static disorder, coupling of the localized excitons to vibrations in the host medium, a possible nonequilibrium of the subsystem of localized Frenkel excitons on the time scale of the emission process, and different excitation conditions (resonant or nonresonant). A Pauli master equation, with microscopically calculated transition rates, is used to describe the redistribution of the exciton population over the manifold of localized exciton states. We find a counterintuitive nonmonotonic temperature dependence of the Stokes shift. In addition, we show that depending on experimental conditions, the observed fluorescence decay time may be determined by vibration-induced intraband relaxation, rather than radiative relaxation to the ground state. The model considered has relevance to a wide variety of materials, such as linear molecular aggregates, conjugated polymers, and polysilanes.     

Photoelectron energy distribution measurements from benzene in rare gas matrices

Photoelectronic energy distributions (PED's) are presented for benzene molecules embedded in solid Ar, Kr and Xe rare gas matrices obtained with monochromatized synchrotron radiation for selective excitation in the range hν = 8 eV to 15 eV. For photon energies in the transparent region of the matrices direct emission from the occupied benzene initial states in the band gap of the matrix is observed. Energy transfer from the matrix exciton states to the benzene guest molecules takes place when the host exciton states are excited. The PED's show that energy of unrelaxed excitons is transferred and that transfer to initial states just at the ionization threshold is favoured.     

Mechanism and origin of exciton spin relaxation in CdSe nanorods

The dynamics of exciton spin relaxation in CdSe nanorods of various sizes and shapes are measured by an ultrafast transient polarization grating technique. The measurement of the third-order transient grating (3-TG) signal utilizing linear cross-polarized pump pulses enables us to monitor the history of spin relaxation among the bright exciton states with a total angular momentum of F = +/-1. From the measured exciton spin relaxation dynamics, it is found that the effective mechanism of exciton spin relaxation is sensitive to the size of the nanorod. Most of the measured cross-polarized 3-TG signals show single-exponential spin relaxation dynamics, while biexponential spin relaxation dynamics are observed in the nanorod of the largest diameter. This analysis suggests that a direct exciton spin flip process between the bright exciton states with F = +/-1 is the dominant spin relaxation mechanism in small nanocrystals, and an indirect spin flip via the dark states with F = +/-2 contributes as the size of the nanocrystal increases. This idea is examined by simulations of 3-TG signals with a kinetic model for exciton spin relaxation considering the states in the exciton fine structure. Also, it is revealed that the rate of exciton spin relaxation has a strong correlation with the diameter, d, of the nanorod, scaled by the power law of 1/d4, rather than other shape parameters such as length, volume, or aspect ratio.     

Katalytische Cyclisierung von Acetylen und substituiertem Acetylen zu aromatischen Kohlenwasserstoffen

The pentahalogenides of niobium and tantalum and some tungsten chlorides catalize the cyclotrimerization of acetylenic hydrocarbons to form aromatic compounds. Acetylene is converted into benzene at atmospheric pressure and temperatures between — 20 and 130°C. Under similar conditions methylacetylene and but-1-yne respectively yield a mixture of the corresponding 1,2,4- and 1,3,5-substituted benzenes while with but-2-yne hexamethyl benzene is obtained. Cocyclization between acetylene and substituted acetylenes or diacetylene is possible; in this case mono- and disubstituted benzenes or biphenyl, terphenyl, and polyphenyls are formed.     

ODMR and triplet state kinetics of a carbazolyl substituted diacetylene crystal

Carbazolyl substituted diacetylene (DCH) monomer crystals showing phosphorescence from four traps have been investigated by optically detected magnetic resonance (ODMR) at 1.2 K. These localized triplet states are attributed to the carbazolyl side groups. Their population and depopulation rate constants and zero field splitting parameters (0.097 <|D|< 0.1002 cm^?1; 0.0068 <|E|<0.0105 cm^?1) have been determined. The results suggest that the traps are disturbed substituents. The proposed interaction of the trap states with an exciton band at 23926 cm^?1 is supported by temperature dependent lifetime measurements.     

Nonmonotonic energy harvesting efficiency in biased exciton chains

We theoretically study the efficiency of energy harvesting in linear exciton chains with an energy bias, where the initial excitation is taking place at the high-energy end of the chain and the energy is harvested (trapped) at the other end. The efficiency is characterized by means of the average time for the exciton to be trapped after the initial excitation. The exciton transport is treated as the intraband energy relaxation over the states obtained by numerically diagonalizing the Frenkel Hamiltonian that corresponds to the biased chain. The relevant intraband scattering rates are obtained from a linear exciton-phonon interaction. Numerical solution of the Pauli master equation that describes the relaxation and trapping processes reveals a complicated interplay of factors that determine the overall harvesting efficiency. Specifically, if the trapping step is slower than or comparable to the intraband relaxation, this efficiency shows a nonmonotonic dependence on the bias: it first increases when introducing a bias, reaches a maximum at an optimal bias value, and then decreases again because of dynamic (Bloch) localization of the exciton states. Effects of on-site (diagonal) disorder, leading to Anderson localization, are addressed as well.     

Exciton dynamics of GaSe nanoparticle aggregates

Time-resolved and static spectroscopic results on GaSe nanoparticle aggregates are presented to elucidate the exciton relaxation and diffusion dynamics. These results are obtained in room-temperature TOP/TOPO solutions at various concentrations. The aggregate absorption spectra are interpreted in terms of electrostatic coupling and covalent interactions between particles. The spectra at various concentrations may then be interpreted in terms of aggregate distributions calculated from a simple equilibrium model. These distributions are used to interpret concentration-dependent emission anisotropy kinetics and time-dependent emission spectral shifts. The emission spectra are reconstructed from the static emission spectra and decay kinetics obtained at a range of wavelengths. The results indicate that the aggregate z axis persistence length is about 9 particles. The results also show that the one-dimensional exciton diffusion coefficient is excitation wavelength dependent and has a value of about 2 x 10(-5) cm(2)/s following 406 nm excitation. Although exciton diffusion results in very little energy relaxation, subsequent hopping of trapped electron/hole pairs occurs by a Forster mechanism and strongly red shifts the emission spectrum.     

Intramolecular Charge Transfer of Carotene‐porphyrin‐fullerene Triad: Sequential or Superexchange Cechanism

As an excellent artificial photosynthetic reaction center, the carotene (C)‐porphyrin (P)‐fullerene (F) triad was extensively investigated experimentally. To reveal the mechanism of the intramolecular charge transfer (ICT) on the mimic of photosynthetic solar energy conversion (such as singlet energy transfer between pigments, and photoinduced electron transfer from excited singlet states to give long‐lived charge‐separated states), the ICT mechanisms of C‐P‐F triad on the exciton were theoretically studied with quantum chemical methods as well as the 2D and 3D real space analysis approaches. The results of quantum chemical methods reveal that the excited states are the ICT states, since the densities of HOMO are localized in the carotene or porphyrin unit, and the densities of LUMO are localized in the fullerene unit. Furthermore, the excited states should be the intramolecular superexchange charge transfer (ISCT) states for the orbital transition from the HOMO whose densities are localized in the carotene to the LUMO whose densities are localized in the fullerene unit. The 3D charge difference densities can clearly show that some excited states are ISCT excited states, since the electron and hole are resident in the fullerene and carotene units, respectively. From the results of the electron‐hole coherence of the 2D transition density matrix, not only 3D results are supported, but also the delocalization size on the exciton can be observed. These phenomena were further interpreted with non‐linear optical effect. The large changes of the linear and non‐linear polarizabilities on the exciton result in the charge separate states, and if their changes are large enough, the ICT mechanism can become the ISCT on the exciton.     

How electron delocalization influences the electron-withdrawing properties of isomeric benzobischalcogenadiazoles

The fermionic potential and delocalization indices for benzo-bis-1,2,5-chalcogenadiazoles reveal inhomogeneous electron delocalization in their benzene ring, which results in compactly localized lone electron pairs on the chalcogen atoms. These features of (de)localization are rooted in a local increase in the kinetic component of the electron correlation, which expresses the Fermi hole variability and the kinetic potential response to electron density variations in the benzene ring of benzobis-1,2,5-chalcogenadiazoles. This explains their better electron-withdrawing properties compared to benzobis-1,2,3-chalcogenadiazoles     

Density matrix approach to orbital relaxation dynamics in ionization

Dynamical response of electrons to a hole generated during ionization is formulated in time domain with the density matrix equations in the time‐dependent unrestricted Hartree–Fock approximation. Time evolutions of orbital energies and electron‐density distributions are computed for K‐shell and M‐shell ionizations of a Na atom by taking into account nonlinear coupling of density matrices beyond linear response. When the hole is generated so slowly that the adiabatic theorem is satisfied, the simulation eventually converges to the state of a fully relaxed Na⁺ ion. A rapid generation of a K‐shell hole (within about 1 fs) leads to a breakdown of the adiabatic theorem, triggering a collective oscillation of the electrons with the period of sub‐femtoseconds. The shake‐up effect associated with strong orbital relaxation in inner‐shell ionization is manifested as a mixing of occupied and unoccupied states in the density matrix.     

Rapid access to amino-substituted quinoline, (di)benzofuran, and carbazole heterocycles through an aminobenzannulation reaction

The use of a powerful aminobenzannulation reaction has been applied for the synthesis of amino-substituted quinolines, dibenzofurans, and carbazoles. The precursors are heterocycles bearing a methyl ketone group ortho to an internal alkyne. They are commercially available or can be obtained in three to four classical and efficient reactions: Vilsmeier-Haack, Sonogashira (diversity point), Grignard, and Ley's oxidation. Upon aminobenzannulation reaction-classical conditions being pyrrolidine neat or in a solvent and 4 A MS-an interesting range of disubstituted quinolines, dibenzofurans, and carbazoles are obtained along with enamine formation in some cases. The reaction is useful since meta-substituted heterocycles are produced and also differs from classical heterocyclic methods which go through closure at the heteroatom-containing ring instead of benzene ring formation.     

Dynamics of unidirectional exciton migration to the molecular periphery in a photoexcited compact dendrimer

We have studied dynamical natures of electronic excited states in a compact series of phenylacetylene dendrimers. So as to clarify the mechanism of unidirectional migration of a photogenerated exciton in a compact dendrimer, we theoretically investigated the temporal behavior of the photogenerated exciton in the molecule by numerically solving the time-dependent Schrodinger equation for the electronic excited states. The structure of the dendrimers is optimized in the ground state, and it is fixed during the calculation of the exciton dynamics. The calculated results show that the exciton generated in the dendrimeric framework tends to migrate toward the outside of the molecule rather than the inside, and to itinerate around the periphery via the through-space interaction between the outer crowding benzene units. This is one of the intrinsic properties that originates from a highly branched treelike structure of the compact dendrimers.     

液晶性直线型共轭芳炔衍生物的合成及电致发光性质

以苯胺和芳炔为基本构筑单元,通过Sonogashira偶联反应, 合成了一种新型含氨基的结构不对称π共轭线性芳炔化合物5-{(6-己氧基萘基)丁二炔}-2-{(4-氨基苯基)乙炔}苄醇。 通过化学修饰在芳炔类小分子端基引入氨基取代基,使其在无吸电子基团存在的条件下通过扭转态的形成实现分子内电荷的有效转移,从而提高芳炔类衍生物电-光转换效率。 同时,通过赋予芳炔类小分子液晶性,有效改善电子与空穴在器件中的电荷平衡,提高器件的效率。 基于氨基取代芳炔衍生物为掺杂发光材料制备的电致发光器件呈现黄绿光发射,器件开启电压较低(7.20 V),显示了较好的电致发光稳定性,器件17.65 V时达到最大亮度126 cd/m²,是一种潜在的电致发光材料。     

Charge transfer in DNA: hole charge is confined to a single base pair due to solvation effects

We include solvation effects in tight-binding Hamiltonians for hole states in DNA. The corresponding linear-response parameters are derived from accurate estimates of solvation energy calculated for several hole charge distributions in DNA stacks. Two models are considered: (A) the correction to a diagonal Hamiltonian matrix element depends only on the charge localized on the corresponding site and (B) in addition to this term, the reaction field due to adjacent base pairs is accounted for. We show that both schemes give very similar results. The effects of the polar medium on the hole distribution in DNA are studied. We conclude that the effects of polar surroundings essentially suppress charge delocalization in DNA, and hole states in (GC)(n) sequences are localized on individual guanines.     

Heterogeneous exciton dynamics revealed by two-dimensional optical spectroscopy

We show that optical two-dimensional (2D) spectroscopy can recover ultrafast heterogeneous dynamics of closely spaced delocalized exciton states from a molecular exciton manifold characterized by a single absorption band. The complete experimental third-order nonlinear optical response from room-temperature J-aggregates in liquid phase is reproduced for the first time with self-consistent Frenkel exciton theory combined with modified Redfield theory. We show that exciton relaxation between the exciton states and nuclear-motion-induced exchange-narrowed energy fluctuations of individual delocalized exciton states can be distinguished because these two processes lead to a distinctively different evolution of the absolute 2D spectrum. Our technique also allows recovery of the variation of the exciton relaxation rates as well as the degree of exciton delocalization across the absorption band.     

Intra- and inter-monomeric transfers in the light harvesting LHCII complex: the Redfield-Förster picture

We further develop the model of energy transfer in the LHCII trimer based on a quantitative fit of the linear spectra (including absorption (OD), linear dichroism (LD), circular dichroism (CD), and fluorescence (FL)) and transient absorption (TA) kinetics upon 650 nm and 662 nm excitation. The spectral shapes and relaxation/migration rates have been calculated using the combined Redfield-F?rster approach capable of correctly describing fast relaxation within strongly coupled chlorophyll (Chl) a and b clusters and slow migration between them. Within each monomeric subunit of the trimeric complex there is fast (sub-ps) conversion from Chl's b to Chl's a at the stromal side accompanied by slow (>10 ps) equilibration between the stromal- and lumenal-side Chl a clusters in combination with slow (>13 ps) population of Chl's a from the 'bottleneck' Chl a604 site. The connection between monomeric subunits is determined by exciton coupling between the stromal-side Chl's b from the two adjacent subunits (Chl b601'-608-609 cluster) making a simultaneous fast (sub-ps) population of the Chl's a possible from both subunits. Final equilibration occurs via slow (>20 ps) migration between the Chl a clusters located on different monomeric subunits. This migration includes up-hill transfers from the red-most Chl a610-611-612 clusters located at the peripheral side in each subunit to the Chl a602-603 dimers located at the inner side of the trimeric LHCII complex.     

Exciton dissociation dynamics in model donor-acceptor polymer heterojunctions. I. Energetics and spectra

In this paper we consider the essential electronic excited states in parallel chains of semiconducting polymers that are currently being explored for photovoltaic and light-emitting diode applications. In particular, we focus upon various type II donor-acceptor heterojunctions and explore the relation between the exciton binding energy to the band offset in determining the device characteristic of a particular type II heterojunction material. As a general rule, when the exciton binding energy is greater than the band offset at the heterojunction, the exciton will remain the lowest-energy excited state and the junction will make an efficient light-emitting diode. On the other hand, if the offset is greater than the exciton binding energy, either the electron or hole can be transferred from one chain to the other. Here we use a two-band exciton to predict the vibronic absorption and emission spectra of model polymer heterojunctions. Our results underscore the role of vibrational relaxation and suggest that intersystem crossings may play some part in the formation of charge-transfer states following photoexcitation in certain cases.