Spectroscopy and femtosecond dynamics of type-II CdTe/CdSe core-shell quantum dots.

Syntheses of CdTe/CdSe type-II quantum dots (QDs) using CdO and CdCl2 as precursors for core and shell, respectively, are reported. Characterization was made via near-IR interband emission, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDX), and X-ray diffraction (XRD). Femtosecond fluorescence upconversion measurements on the relaxation dynamics of the CdTe core (in CdTe/CdSe) emission and CdTe/CdSe interband emission reveal that as the size of the core increases from 5.3, 6.1 to 6.9 nm, the rate of photoinduced electron separation decreases from 1.96, 1.44 to 1.07 x10(12) s(-1). The finite rates of the initial charge separation are tentatively rationalized by the small electron-phonon coupling, causing weak coupling between the initial and charge-separated states.     

微波辅助溶剂热法制备Pt/石墨烯-TiO2及其催化性能

质子交换膜燃料电池具有比能量高、结构简单、工作温度低、高效清洁和安静无摩擦等优点,是一种非常具有发展前景的电源.燃料电池借用电催化剂把燃料与氧化剂中的化学能转化为电能,通常采用碳粉负载的Pt催化剂.在燃料电池的工作环境下,碳粉载体容易腐蚀和团聚,降低了催化剂活性和稳定性,进而降低了燃料电池的使用寿命.因此,探索高稳定性的催化剂载体有利于提高催化剂的稳定性,促进燃料电池的实用化进程.为增强催化剂载体的抗腐蚀能力,一些金属氧化物如SnO2,WO3,CeO2和TiO2等被用作催化剂载体.其中,TiO2因具有稳定的化学性能以及与金属之间的"强相互作用"而备受研究者关注.但TiO2载体比表面积小和导电能力弱等缺点限制了它在燃料电池中的应用.石墨烯具有卓越的导电性和比表面积,却容易发生团聚.利用TiO2与碳材料间存在的协同作用,将TiO2与石墨烯复合来制备复合载体,能够增强TiO2的导电能力,抑制石墨烯的团聚,提高催化剂载体的化学稳定性和比表面积.本文采用微波辅助溶剂热法制备了石墨烯-TiO2复合载体和Pt/石墨烯-TiO2催化剂,研究了TiO2含量对催化剂活性和稳定性的影响.采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对制备的样品进行了微观结构和成分表征.结果表明,Pt/石墨烯-TiO2催化剂中TiO2为立方状纳米颗粒,粒径约为60 nm,均匀地分布在石墨烯上;Pt纳米粒子倾向于锚定在TiO2与石墨烯之间,而且分布均匀.采用线性伏安扫描(LSV)和循环伏安法(CV)测试了不同TiO2含量的Pt/石墨烯-TiO2催化剂的活性和稳定性.发现TiO2的加入确实能够提高催化剂的稳定性,随着TiO2含量的提高,催化剂稳定性增加.当TiO2含量为20%时,催化剂的起始电压与极限电流均与Pt/C催化剂接近.经过循环伏安扫描3000圈的快速老化测试后,Pt/石墨烯-TiO2催化剂起始电压的负移明显低于Pt/C催化剂,呈现了优良的稳定性和催化活性.     

Influence of thermal fluctuations on interfacial electron transfer in functionalized TiO2 semiconductors

The influence of thermal fluctuations on the dynamics of interfacial electron transfer in sensitized TiO2-anatase semiconductors is investigated by combining ab initio DFT molecular dynamics simulations and quantum dynamics propagation of transient electronic excitations. It is shown that thermal nuclear fluctuations speed up the underlying interfacial electron transfer dynamics by introducing nonadiabatic transitions between electron acceptor states, localized in the vicinity of the photoexcited adsorbate, and delocalized states extended throughout the semiconductor material, creating additional relaxation pathways for carrier diffusion. Furthermore, it is shown that room-temperature thermal fluctuations reduce the anisotropic character of charge diffusion along different directions in the anatase crystal and make similar the rates for electron injection from adsorbate states of different character. The reported results are particularly relevant to the understanding of temperature effects on surface charge separation mechanisms in molecular-based photo-optic devices.     

石墨烯-二氧化钛复合催化剂对光催化性能的提高(英文)

以石墨烯氧化物和钛酸四丁酯为原料,通过水热法、无氧煅烧转晶合成了graphene-TiO2复合催化剂,并采用透射电镜、X射线衍射、拉曼光谱和X射线光电子能谱等手段对其进行了表征.结果表明,TiO2全部为锐钛矿晶型,呈纳米颗粒状附着在薄膜状的graphene表面.以亚甲基蓝为目标物,评价了graphene-TiO2催化剂的光催化性能.结果表明,graphene-TiO2的光催化降解能力明显优于相同方法制备的纳米TiO2颗粒,且具有较好的稳定性,空穴在降解过程中起主要作用,碱性溶液更有利于催化剂对MB的降解.     

Quantum dynamics simulations of interfacial electron transfer in sensitized TiO2 semiconductors

Ab initio DFT molecular dynamics simulations are combined with quantum dynamics calculations of electronic relaxation to investigate the interfacial electron transfer in catechol/TiO(2)-anatase nanostructures under vacuum conditions. It is found that the primary process in the interfacial electron-transfer dynamics involves an ultrafast (tau(1) approximately 6 fs) electron-injection event that localizes the charge in the Ti(4+) surface ions next to the catechol adsorbate. The primary event is followed by charge delocalization (i.e., carrier diffusion) through the TiO(2)-anatase crystal, an anisotropic diffusional process that can be up to an order of magnitude slower along the [-101] direction than carrier relaxation along the [010] and [101] directions in the anatase crystal. It is shown that both the mechanism of electron injection and the time scales for interfacial electron transfer are quite sensitive to the symmetry of the electronic state initially populated in the adsorbate molecule. The results are particularly relevant to the understanding of surface charge separation in efficient mechanisms of molecular-based photovoltaic devices.     

Vibronic interactions and possible electron pairing in the photoinduced excited electronic States in molecular systems: a theoretical study

Electron-phonon interactions in the photoinduced excited electronic states in molecular systems such as phenanthrene-edge-type hydrocarbons are discussed and compared with those in the monoanions and cations. The complete phase patterns difference between the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO) (the atomic orbitals between two neighboring carbon atoms combined in phase (out of phase) in the HOMO are combined out of phase (in phase) in the LUMO) are the main reason that the C-C stretching modes around 1500 cm(-1) afford much larger electron-phonon coupling constants in the excited electronic states than in the charged electronic states. The frequencies of the vibrational modes that play an essential role in the electron-phonon interactions for the excited electronic states are similar to those for the monoanions and cations in phenanthrene-edge-type hydrocarbons. Possible electron pairing and Bose-Einstein condensation in the photoinduced excited electronic states as well as those in the monoanions and cations in molecular systems such as phenanthrene-edge-type hydrocarbons are also discussed.     

Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study

Charge separation is one of the most crucial processes in photochemical dynamics of energy conversion, widely observed ranging from water splitting in photosystem II (PSII) of plants to photoinduced oxidation reduction processes. Several basic principles, with respect to charge separation, are known, each of which suffers inherent charge recombination channels that suppress the separation efficiency. We found a charge separation mechanism in the photoinduced excited-state proton transfer dynamics from Mn oxides to organic acceptors. This mechanism is referred to as coupled proton and electron wave-packet transfer (CPEWT), which is essentially a synchronous transfer of electron wave-packets and protons through mutually different spatial channels to separated destinations passing through nonadiabatic regions, such as conical intersections, and avoided crossings. CPEWT also applies to collision-induced ground-state water splitting dynamics catalyzed by Mn₄CaO₅ cluster. For the present photoinduced charge separation dynamics by Mn oxides, we identified a dynamical mechanism of charge recombination. It takes place by passing across nonadiabatic regions, which are different from those for charge separations and lead to the excited states of the initial state before photoabsorption. This article is an overview of our work on photoinduced charge separation and associated charge recombination with an additional study. After reviewing the basic mechanisms of charge separation and recombination, we herein studied substituent effects on the suppression of such charge recombination by doping auxiliary atoms. Our illustrative systems are X–Mn(OH)₂ tied to N-methylformamidine, with X=OH, Be(OH)₃, Mg(OH)₃, Ca(OH)₃, Sr(OH)₃ along with Al(OH)₄ and Zn(OH)₃. We found that the competence of suppression of charge recombination depends significantly on the substituents. The present study should serve as a useful guiding principle in designing the relevant photocatalysts.     

C60 in intense short pulse laser fields down to 9 fs: excitation on time scales below e-e and e-phonon coupling

The interaction of C60 fullerenes with 765-797 nm laser pulses as short as 9 fs at intensities of up to 3.7 x 10(14) W cm(-2) is investigated with photoion spectroscopy. The excitation time thus addressed lies well below the characteristic time scales for electron-electron and electron-phonon couplings. Thus, energy deposition into the system is separated from energy redistribution among the various electronic and nuclear degrees of freedom. Insight into fundamental photoinduced processes such as ionization and fragmentation is obtained from the analysis of the resulting mass spectra as a function of pulse duration, laser intensity, and time delay between pump and probe pulses, the latter revealing a memory effect for storing electronic energy in the system with a relaxation time of about 50 fs. Saturation intensities and relative abundances of (multiply charged) parent and fragment ions (C60(q+), q=1-6) are fingerprints for the ionization and fragmentation mechanisms. The observations indicate that for final charge states q>1 the well known C60 giant plasmon resonance is involved in creating ions and a significant amount of large fragments even with 9 fs pulses through a nonadiabatic multielectron dynamics. In contrast, for energetic reasons singly charged ions are generated by an essentially adiabatic single active electron mechanism and negligible fragmentation is found when 9 fs pulses are used. These findings promise to unravel a long standing puzzle in understanding C60 mass spectra generated by intense femtosecond laser pulses.     

Electron transfer dynamics from organic adsorbate to a semiconductor surface: zinc phthalocyanine on TiO2(110)

The femtosecond time evolutions of excited states in zinc phthalocyanine (ZnPC) films and at the interface with TiO2(110) have been studied by using time-resolved two-photon photoelectron spectroscopy (TR-2PPE). The excited states are prepared in the first singlet excited state (S1) with excess vibrational energy. Two different films are examined: ultrathin (monolayer) and thick films of approximately 30 A in thickness. The decay behavior depends on the thickness of the film. In the case of the thick film, TR-2PPE spectra are dominated by the signals from ZnPC in the film. The excited states decay with tau = 118 fs mainly by intramolecular vibrational relaxation. After the excited states cascaded down to near the bottom of the S1 manifold, they decay slowly (tau = 56 ps) although the states are located at above the conduction band minimum of the bulk TiO2. The exciton migration in the thick film is the rate-determining step for the electron transfer from the film to the bulk TiO2. In the case of the ultrathin film, the contribution of electron transfer is more evident. The excited states decay faster than those in the thick film, because the electron transfer competes with the intramolecular relaxation processes. The electronic coupling with empty bands in the conduction band of TiO2 plays an important role in the electron transfer. The lower limit of the electron-transfer rate was estimated to be 1/296 fs(-1). After the excited states relax to the states whose energy is below the conduction band minimum of TiO2, they decay much more slowly because the electron-transfer channel is not available for these states.     

Charge and energy dynamics in photo-excited poly(para-phenylenevinylene) systems

We report results from simulations of charge and energy dynamics in poly(para-phenylenevinylene) (PPV) and PPV interacting with C60. The simulations were performed by solving the time-dependent Schrodinger equation and the lattice equation of motion simultaneously and nonadiabatically. The electronic system and the coupling of the electrons to the lattice were described by an extended three-dimensional version of the Su-Schrieffer-Heeger model, which also included an external electric field. Electron and lattice dynamics following electronic excitations at different energies have been simulated. The effect of additional lattice energy was also included in the simulations. Our results show that both exciton diffusion and transitions from high to lower lying excitations are stimulated by increasing the lattice energy. Also field induced charge separation occurs faster if the lattice energy is increased. This separation process is highly nonadiabatic and involves a significant rearrangement of the electron distribution. In the case of PPV coupled to C60, we observe a spontaneous charge separation. The separation time is in this case limited by the local concentration of C60 molecules close to the PPV chain.     

Conformationally constrained macrocyclic diporphyrin-fullerene artificial photosynthetic reaction center

Photosynthetic reaction centers convert excitation energy from absorbed sunlight into chemical potential energy in the form of a charge-separated state. The rates of the electron transfer reactions necessary to achieve long-lived, high-energy charge-separated states with high quantum yields are determined in part by precise control of the electronic coupling among the chromophores, donors, and acceptors and of the reaction energetics. Successful artificial photosynthetic reaction centers for solar energy conversion have similar requirements. Control of electronic coupling in particular necessitates chemical linkages between active component moieties that both mediate coupling and restrict conformational mobility so that only spatial arrangements that promote favorable coupling are populated. Toward this end, we report the synthesis, structure, and photochemical properties of an artificial reaction center containing two porphyrin electron donor moieties and a fullerene electron acceptor in a macrocyclic arrangement involving a ring of 42 atoms. The two porphyrins are closely spaced, in an arrangement reminiscent of that of the special pair in bacterial reaction centers. The molecule is produced by an unusual cyclization reaction that yields mainly a product with C(2) symmetry and trans-2 disubstitution at the fullerene. The macrocycle maintains a rigid, highly constrained structure that was determined by UV-vis spectroscopy, NMR, mass spectrometry, and molecular modeling at the semiempirical PM6 and DFT (B3LYP/6-31G**) levels. Transient absorption results for the macrocycle in 2-methyltetrahydrofuran reveal photoinduced electron transfer from the porphyrin first excited singlet state to the fullerene to form a P(?+)-C(60)(?-)-P charge separated state with a time constant of 1.1 ps. Photoinduced electron transfer to the fullerene excited singlet state to form the same charge-separated state has a time constant of 15 ps. The charge-separated state is formed with a quantum yield of essentially unity and has a lifetime of 2.7 ns. The ultrafast charge separation coupled with charge recombination that is over 2000 times slower is consistent with a very rigid molecular structure having a small reorganization energy for electron transfer, relative to related porphyrin-fullerene molecules.     

Competing electron-transfer pathways in hydrocarbon frameworks: short-circuiting through-bond coupling by nonbonded contacts in rigid U-shaped norbornylogous systems containing a cavity-bound aromatic pendant group

This work explores electron transfer through nonbonded contacts in two U-shaped DBA molecules 1DBA and 2DBA by measuring electron-transfer rates in organic solvents of different polarities. These molecules have identical U-shaped norbornylogous frameworks, 12 bonds in length and with diphenyldimethoxynaphthalene (DPMN) donor and dicyanovinyl (DCV) acceptor groups fused at the ends. The U-shaped cavity of each molecule contains an aromatic pendant group of different electronic character, namely p-ethylphenyl, in 1DBA, and p-methoxyphenyl, in 2DBA. Electronic coupling matrix elements, Gibbs free energy, and reorganization energy were calculated from experimental photophysical data for these compounds, and the experimental results were compared with computational values. The magnitude of the electronic coupling for photoinduced charge separation, /V(CS)/, in 1DBA and 2DBA were found to be 147 and 274 cm(-1), respectively, and suggests that the origin of this difference lies in the electronic nature of the pendant aromatic group and charge separation occurs by tunneling through the pendant group, rather than through the bridge. 2DBA, but not 1DBA, displayed charge transfer (CT) fluorescence in nonpolar and weakly polar solvents, and this observation enabled the electronic coupling for charge recombination, /V(CR)/, in 2DBA to be made, the magnitude of which is approximately 500 cm(-1), significantly larger than that for charge separation. This difference is explained by changes in the geometry of the molecule in the relevant states; because of electrostatic effects, the donor and acceptor chromophores are about 1 A closer to the pendant group in the charge-separated state than in the locally excited state. Consequently the through-pendant-group electronic coupling is stronger in the charge-separated state--which controls the CT fluorescence process--than in the locally excited state--which controls the charge separation process. The magnitude of /V(CR)/ for 2DBA is almost 2 orders of magnitude greater than that in DMN-12-DCV, having the same length bridge as for the former molecule, but lacking a pendant group. This result unequivocally demonstrates the operation of the through-pendant-group mechanism of electron transfer in the pendant-containing U-shaped systems of the type 1DBA and 2DBA.     

The origin of unidirectional charge separation in photosynthetic reaction centers: nonadiabatic quantum dynamics of exciton and charge in pigment–protein complexes

Exciton charge separation in photosynthetic reaction centers from purple bacteria (PbRC) and photosystem II (PSII) occurs exclusively along one of the two pseudo-symmetric branches (active branch) of pigment–protein complexes. The microscopic origin of unidirectional charge separation in photosynthesis remains controversial. Here we elucidate the essential factors leading to unidirectional charge separation in PbRC and PSII, using nonadiabatic quantum dynamics calculations in conjunction with time-dependent density functional theory (TDDFT) with the quantum mechanics/molecular mechanics/polarizable continuum model (QM/MM/PCM) method. This approach accounts for energetics, electronic coupling, and vibronic coupling of the pigment excited states under electrostatic interactions and polarization of whole protein environments. The calculated time constants of charge separation along the active branches of PbRC and PSII are similar to those observed in time-resolved spectroscopic experiments. In PbRC, Tyr-M210 near the accessary bacteriochlorophyll reduces the energy of the intermediate state and drastically accelerates charge separation overcoming the electron–hole interaction. Remarkably, even though both the active and inactive branches in PSII can accept excitons from light-harvesting complexes, charge separation in the inactive branch is prevented by a weak electronic coupling due to symmetry-breaking of the chlorophyll configurations. The exciton in the inactive branch in PSII can be transferred to the active branch via direct and indirect pathways. Subsequently, the ultrafast electron transfer to pheophytin in the active branch prevents exciton back transfer to the inactive branch, thereby achieving unidirectional charge separation.

Essential factors leading to unidirectional charge separation in photosynthetic reaction centers are clarified via nonadiabatic quantum dynamics calculations.     

Atomistic mechanism of charge separation upon photoexcitation at the dye-semiconductor interface for photovoltaic applications

Charge separation in excited states upon visible light absorption is a central process in photovoltaic solar cell applications. Employing state-of-the-art first principles calculations based on time-dependent density functional theory (TDDFT), we simulate electron-hole dynamics in real time and illustrate the microscopic mechanism of charge separation at the interface between organic dye molecules and oxide semiconductor surfaces in dye-sensitized solar cells. We found that electron-hole separation proceeds non-adiabatically on an ultrafast timescale <100 fs at an anthocyanin/TiO(2) interface, and it is strongly mediated by the vibrations of interface Ti-O bonds, which anchor the dye onto the TiO(2) surface. The obtained absorption spectrum and electron injection timescale agree with experimental measurements.     

Quantized time correlation function approach to nonadiabatic decay rates in condensed phase: application to solvated electrons in water and methanol

A new, alternative form of the golden rule formula defining the nonadiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the nonadiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via molecular dynamics simulations. The formalism is applied to the problem of the nonadiabatic p-->s relaxation of an equilibrated p-electron in water and methanol. We find that, in both solvents, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated nonadiabatic coupling.     

Exploring the Franck–Condon region of a photoexcited charge transfer complex in solution to interpret femtosecond stimulated Raman spectroscopy: excited state electronic structure methods to unveil non-radiative pathways

We present electronic structure methods to unveil the non-radiative pathways of photoinduced charge transfer (CT) reactions that play a main role in photophysics and light harvesting technologies. A prototypical π-stacked molecular complex consisting of an electron donor (1-chloronaphthalene, 1ClN) and an electron acceptor (tetracyanoethylene, TCNE) was investigated in dichloromethane solution for this purpose. The characterization of TCNE:π:1ClN in both its equilibrium ground and photoinduced low-lying CT electronic states was performed by using a reliable and accurate theoretical–computational methodology exploiting ab initio molecular dynamics simulations. The structural and vibrational time evolution of key vibrational modes is found to be in excellent agreement with femtosecond stimulated Raman spectroscopy experiments [R. A. Mathies et al., J. Phys. Chem. A, 2018, 122, 14, 3594], unveiling a correlation between vibrational fingerprints and electronic properties. The evaluation of nonadiabatic coupling matrix elements along generalized normal modes has made possible the interpretation on the molecular scale of the activation of nonradiative relaxation pathways towards the ground electronic state. In particular, two low frequency vibrational modes such as the out of plane bending and dimer breathing and the TCNE central C C stretching play a prominent role in relaxation phenomena from the electronic CT state to the ground state one.

We present electronic structure methods to unveil the non-radiative pathways of photoinduced charge transfer (CT) reactions that play a main role in photophysics and light harvesting technologies.     

9,10-二氰基蒽和杜烯间光诱导电子转移的电荷分离态和电子耦合

采用从头算方法,讨论了9,10-二氰基蒽(DCA)和杜烯(DUR)间光诱导电子转移反应的态-态跃迁.考虑基组重叠误差(BSSE)对相互作用能的校正,用MP₂方法优化得到重叠式[DCA…DUR]配合物的稳定构型.用单激发组态相互作用(CIS)方法讨论了[DCA…DUR]配合物的光诱导电荷分离和电荷复合过程.根据广义Mulliken-Hush(GMH)模型,计算了电荷复合过程的电子耦合矩阵元.结果表明,[DCA…DUR]配合物的S₀→S₁和S₀→S₂跃迁产生了两个强的局域激发态,S₀→S₃跃迁直接导致电荷分离态,小的振子强度预测该电荷转移(CT)跃迁是一弱跃迁,电荷分离态S₃衰变到低局域激发态或基态的电荷复合是可能的.