Probing inhomogeneous vibrational reorganization energy barriers of interfacial electron transfer

An atomic force microscopy (AFM) and confocal Raman microscopy study of the interfacial electron transfer of a dye-sensitization system, i.e., alizarin adsorbed upon TiO(2) nanoparticles, has revealed the distribution of the mode-specific vibrational reorganization energies encompassing different local sites ( approximately 250-nm spatial resolution). Our experimental results suggest inhomogeneous vibrational reorganization energy barriers and different Franck-Condon coupling factors of the interfacial electron transfer. The total vibrational reorganization energy was inhomogeneous from site to site; specifically, mode-specific analyses indicated that energy distributions were inhomogeneous for bridging normal modes and less inhomogeneous or homogeneous for nonbridging normal modes, especially for modes far away from the alizarin-TiO(2) coupling hydroxyl modes. The results demonstrate a significant step forward in characterizing site-specific inhomogeneous interfacial charge-transfer dynamics.     

Structural changes upon photoexcitation into the metal-to-ligand charge-transfer state of [Cu(pqx)(PPh3)2]+ probed by resonance Raman spectroscopy and density functional theory

The structural changes that occur when [Cu(pqx)(PPh(3))(2)](+) (pqx is 2-(2'-pyridyl)quinoxaline) undergoes excitation through a metal-to-ligand charge-transfer (MLCT) transition are investigated using resonance Raman excitation profiles coupled with density functional theory (DFT). The DFT calculations predict bond lengths to within 3 pm and absolute deviations of 7 cm(-1) for the vibrational frequencies of [Cu(pqx)(PPh(3))(2)](+). TD-DFT calculations of oscillator strengths (f = 0.089) and band positions (419 nm) showed close agreement with experiment (f = 0.07, 431 nm). Resonance Raman spectra show the 527 cm(-1) (nu(29)) and 1476 cm(-1) (nu(75)) modes undergo the largest dimensionless displacement (Delta = 1.5 and 1.1, respectively) following photoexcitation into the MLCT Franck-Condon region. The solvent couples strongly to the MLCT transition and resonance Raman intensity analysis (RRIA) gives a solvent reorganization energy of 3400 cm(-1) for dichloromethane and 2800 cm(-1) for chloroform solutions. A large inner-sphere reorganization of 3430 cm(-1) in dichloromethane solution (3520 cm(-1) in chloroform solution) was found for [Cu(pqx)(PPh(3))(2)](+), indicating that the molecule as a whole undergoes significant distortion following MLCT excitation.     

Solvent effects on interfacial electron transfer from Ru(4,4'-dicarboxylic acid-2,2'-bipyridine)2(NCS)2 to nanoparticulate TiO2: spectroscopy and solar photoconversion

Resonance Raman spectra are reported for Ru(4,4'-dicarboxylic acid-2,2'-bipyridine)2(NCS)2 (commonly called "N3") in ethanol solution and adsorbed on nanoparticulate colloidal TiO2 in ethanol (EtOH) and in acetonitrile (ACN), at wavelengths within the visible absorption band of the dye. Raman cross sections of free N3 in EtOH are found to be similar to those of N3 adsorbed on colloidal TiO2 in EtOH, and are generally lower than those of N3 on TiO2 in ACN. Strong electronic coupling mediated by surface states results in red-shifted absorption spectra and enhanced Raman signals for N3 adsorbed on nanocolloidal TiO2 in ACN compared to EtOH. In contrast, the absorption spectrum of N3 on nanocrystalline TiO2 in contact with solvent is similar for ACN and EtOH. Wavelength-dependent depolarization ratios for N3 Raman bands of both free and adsorbed N3 reveal resonance enhancement via two or more excited electronic states. Luminescence spectra of N3 adsorbed on nanocrystalline films of TiO2 and ZrO2 in contact with solvent reveal that the quantum yield of electron injection phi(ET) into TiO2 decreases in the order ACN > EtOH > DMSO. Dye-sensitized solar cells were fabricated with N3 adsorbed on nanocrystalline films of TiO2 in contact with ACN, EtOH, and DMSO solutions containing LiI/LiI3 electrolyte. Photoconversion efficiencies eta were found to be 2.6% in ACN, 1.3% in DMSO, and 0.84% in EtOH. Higher short circuit currents are found in cells using ACN, while the maximum voltage is found to be largest in DMSO. It is concluded that the increased photocurrent and quantum yield of interfacial electron transfer in acetonitrile as compared to ethanol and DMSO is primarily the result of faster electron injection of N3 when adsorbed on TiO2 in the presence of ACN as opposed to EtOH or DMSO.     

Surface-enhanced Raman scattering and surface-enhanced resonance Raman scattering excitation profiles of Ag-2,2'-bipyridine surface complexes and of [Ru(bpy)3]2+ on Ag colloidal surfaces: manifestations of the charge-transfer resonance contributions to the overall surface enhancement of Raman scattering

Excitation profiles of SERS (surface-enhanced Raman scattering) and/or SERRS (surface-enhanced resonance Raman scattering) spectral bands of two forms of a Ag-bpy (bpy = 2,2'-bipyridine) surface complex and of [Ru(bpy)3]2+ on Ag nanoparticle (hydrosol) surfaces were determined from the spectra excited in the 458-600 nm region and are reported together with the FT-SERS spectra of the Ag-bpy surface complex and FT Raman spectra of [Ru(bpy)3] Cl2. Seven of the observed 11 fundamentals as well as their first overtones and combination bands are selectively enhanced in SERS of the Ag-bpy surface complex formed in the Ag colloid/HCl/bpy system. The profiles of these bands show a common maximum at approximately 540 nm. The selectively enhanced bands of the Ag-bpy surface complex have nearly the same wavenumbers as those enhanced in the SERRS and resonance Raman spectra of [Ru(bpy)3]2+ upon excitation close to the 453 nm maximum of its MLCT absorption band. Moreover, the intensity patterns of the bpy vibrations of the two species match both in resonance (541 nm excitation for Ag-bpy, 458 nm for [Ru(bpy)3]2+) and in off-resonance (458 and 1064 nm for Ag-bpy, 1064 nm for [Ru(bpy)3]2+). The distinct band shapes of the excitation profiles of the selectively enhanced vibrational modes of the Ag-bpy surface complex, as well as the observation of overtones and combination bands in the SERS spectra upon excitation into this "band", are interpreted in terms of a charge-transfer resonance contribution to the overall SERS enhancement. In view of the near-coincidence of the vibrational modes coupled to the resonant electronic transition of Ag-bpy with those coupled to the MLCT transition of [Ru(bpy)3]2+, the resonant electronic transition is tentatively assigned to a Ag metal to bpy (pi*) CT transition.     

Interfacial electron transfer energetics studied by high spatial resolution tip-enhanced Raman spectroscopic imaging

Interfacial electron transfer (ET) in TiO?-based systems is important in artificial solar energy harvesting systems, catalysis, and in advanced oxidative waste water treatment. The fundamental importance of ET processes and impending applications make the study of interfacial ET a promising research area. Photoexcitation of dye molecules adsorbed on the surface of wide band gap semiconductors, such as TiO?, results in the injection of electrons from the dye molecules to the conduction band of the semiconductor or energetically accessible surface electronic states. Using Raman spectroscopy and ensemble-averaging approaches,t he chemical bonding and vibrational relaxation of the ET processes have been extensively studied. However, due to the complexity of the interfacial ET energetics and dynamics, significant questions remain on characterizing the source of the observed complexities. To address these important issues, we have applied advanced spectroscopic and imaging techniques such as confocal and tip-enhanced near-field Raman as well as photoluminescence spectroscopic and topographic imaging. Here we explore single surface states on TiO? as well as the interfacial electronic coupling of alizarin to TiO? single crystalline surfaces.     

Solvent-dependent vibrational frequencies and reorganization energies of two merocyanine chromophores

Absorption and resonance Raman spectra have been measured over a wide range of solvents for two merocyanine dyes containing the indoline ("Fischer" base) electron donor group with different accepting groups. One appears to be near the cyanine limit (equal contributions of the neutral and zwitterionic resonance forms to both ground- and excited-state structures) based on electrooptic absorption data showing a very small dipole moment change upon electronic excitation. The resonance Raman spectra of both molecules show significant frequency shifts and intensity redistributions that evolve monotonically with increasing solvent polarity and are consistent with increasing zwitterionic character of the ground-state structure. The vibrational reorganization energies of both molecules, obtained by simulating the absorption band shapes, are smaller in polar solvents than in nonpolar or weakly polar ones, consistent with a more cyanine-like structure at higher solvent polarities. However, the vibrational reorganization energies of both molecules exceed 700 cm(-1) in all solvents, larger than in many true cyanine dyes, and the optical absorption maxima do not correlate well with either solvent polarity or vibrational reorganization energy. This indicates some limitations to the structural conclusions that can be reached from the two-state model for pi-conjugated donor-acceptor systems.     

Initial excited-state structural dynamics of 2'-deoxyguanosine determined via UV resonance Raman spectroscopy

The resonance Raman spectra of 2'-deoxyguanosine, a DNA nucleoside, were measured in aqueous solution at wavelengths throughout its 260 nm absorption band. Self-consistent analysis of the resulting resonance Raman excitation profiles and absorption spectrum using a time-dependent wave packet formalism with two electronic states yielded the initial excited-state structural dynamics in both states. The vibrational modes containing the N(7)═C(8) stretching and C(8)-H bending internal coordinates were found to exhibit significant initial structural dynamics upon photoexcitation to either state and are coincident with the photochemical reaction coordinate involving the formation of the 2'-deoxyguanosine cation radical.     

Characterization of the adsorption of Ru-bpy dyes on mesoporous TiO2 films with UV-Vis, Raman, and FTIR spectroscopies

In the present work the adsorption of a new dye, [Ru(dcbpyH(2))(2)(bpy-TPA(2))](PF(6))(2), and the well-known (Bu(4)N)(2)[Ru(dcbpyH)(2)(NCS)(2)] complex on mesoporous anatase films were investigated to clarify the role of the carboxylate groups in the anchoring process of the dyes on the semiconductor surface. For this purpose UV-vis, Raman, resonance Raman, and ATR-FTIR spectroscopies have been used. The results of the Raman experiments at different excitation wavelengths demonstrate that photoinduced charge-transfer processes take place efficiently between the adsorbate and the substrate. Moreover, this is the first time that the Raman spectrum of a Ru-bpy dye (in this case, the dye N719) adsorbed on TiO(2) has been obtained without the resonance condition, only by means of SERS enhancement. The coordination of both complexes on the TiO(2) paste films is proposed to occur via bidentate or bridging linkage.     

3-二甲氨基-2-甲基丙烯醛S2激发态结构动力学

采用共振拉曼光谱和完全活性自洽场理论计算研究了3-二甲氨基-2-甲基丙烯醛（DMAMP）光激发到S2（ππ^＊）态后的光物理性能,在B3LYP／6—311＋＋G（d,p）水平计算确定了DMAMP与其三种异构体之间的基态异构化能垒,指认了振动光谱．采用涵盖紫外强吸收带的激光波长,获得了DMAMP在环己烷、乙腈和甲醇溶剂中的A-带共振拉曼光谱,含时密度泛函方法计算确定了该光谱中基频的相对强度,发现振动-电子耦合发生在S2（）态的Franck—Condon区域．CASSCF计算方法确定低单重和三重激发态、势能面锥形交叉点和系间窜跃点的激发能．共振拉曼光谱强度模式分析和CASSCF计算获得了DMAMP的A一带短时结构动力学和其后的衰变动力学表明,C1=06和C2=C3之间的瞬时去共轭效应发生在S2（ππ^＊）态的Franck—Condon区域,激发态电荷重分布机制表明,C3和二甲氨基之间以及C1和C2之间的共轭增强效应发生在波包离开Franck-Condon区域后．C1=06和C2=C3之间的去共轭效应使得-C3=N（CH3）2沿着C2-C3键旋转更加容易,C1-C2之间以及C3和N（CH3）的共轭增强效应使得绕C1-C2和C3-N5旋转变得比较困难．这些表明DMAMP初始结构动力学沿着CI-1（S2／S0）交叉点展开,而沿CI-2（S2／S0）和[CI-3（S2／S0）交叉点展开的几率可以忽略,提出了DMAMP分子受光激发从S2,FC（ππ^＊）经由各锥形交叉点和各系间窜跃点回到S0或T1,min的两个衰变通道。     

N3-dye-induced visible laser anatase-to-rutile phase transition on mesoporous TiO2 films

Titanium dioxide has been extensively used in photocatalysis and dye-sensitized solar cells, where control of the anatase-to-rutile phase transformation may allow the realization of more efficient devices exploiting the synergic effects at anatase/rutile interfaces. Thus, a systematic study showing the proof of concept of a dye-induced morphological transition and an anatase-to-rutile transition based on visible laser (532 nm) and nano/micro patterning of mesoporous anatase (Degussa P25 TiO(2)) films is described for the first time using a confocal Raman microscope. At low laser intensities, only the bleaching of the adsorbed N3 dye was observed. However, high enough temperatures to promote melting/densification processes and create a deep hole at the focus and an extensive phase transformation in the surrounding material were achieved using 1s laser pulses of 25-41 mW/cm(2), in resonance with the MLCT band. The dye was shown to play a key role, being responsible for the absorption and efficient conversion of the laser light into heat. As a matter of fact, the dye is photothermally decomposed to amorphous carbon or to gaseous species (CO(x), NO(x), and H(2)O) under a N(2) or O(2) atmosphere, respectively.     

I2-1-己烯复合物电子转移振动重组能的共振拉曼强度分析

获得了I₂-1-己烯复合物的吸收横截面和绝对共振拉曼横截面.用约270 nm光激发导致复合物的I-I伸缩振动模和C-C伸缩振动模等拉曼基频、泛频及其组合频强度的共振增强.采用含时波包理论的简单模型定量确定I₂-1-己烯复合物的光致电子转移振动重组能和均质展宽.总振动重组能3 744 cm^-1分布于4个振动模,贡献最大是I-I伸缩振动v₁₃,其值为2 490 cm^-1,约占总振动重组能的2/3.其次为C-C伸缩振动v₄₆,其值为1 170 cm^-1,约为总振动重组能的1/3.剩余2%的振动重组能是由烷基CH₃和CH₂的扭转振动v₃₆和v₂₄贡献.     

Decay Dynamics of N,N-Dimethylthioacetamide in S3(ππ*) State (cited: 1)

The decay dynamics of N,N-dimethylthioacetamide after excitation to the S₃(ππ^*) state was studied by using the resonance Raman spectroscopy and complete active space selfconsistent field method calculations. The UV-absorption and vibrational spectra were assigned. The A-band resonance Raman spectra were obtained in acetonitrile, methanol and water with the laser excitation wavelengths in resonance with the first intense absorption band to probe the Franck-Condon region structural dynamics. The CASSCF calculations were carried out to determine the excitation energies and optimized structures of the lowerlying singlet states and conical intersection point. The A-band structural dynamics and the corresponding decay mechanism were obtained by the analysis of the resonance Raman intensity pattern and the CASSCF calculated structural parameters. The major decay channel of _3,FC(ππ^*)→S₃(ππ^*)/S₁(nπ^*)→_{1(nπ^*) is proposed.}     

Resonance Raman analysis of nonlinear solvent dynamics: betaine-30 in ethanol

Resonance Raman profiles for 14 vibrational modes of betaine-30 in ethanol at room temperature were measured at wavelengths within the first charge-transfer absorption band. The absorption spectrum and resonance Raman profiles were analyzed using time-dependent theory and a Brownian oscillator model modified to account for nonlinear solvent response; i.e., dependence of the solvent reorganization energy on the electronic state of the solute. As in our previous study of betaine-30 in acetonitrile, the solvent reorganization energy for the excited electronic state, determined from resonance Raman spectroscopy, was found to be smaller than that for the ground electronic state, determined from the absorption spectrum. The mode-dependent internal reorganization energies of betaine-30 in ethanol were found to be slightly larger than those of betaine-30 in acetonitrile. Temperature-dependent solvent reorganization energies for the ground electronic state were determined from analysis of the absorption line shape from 279 to 332 K and were found to decrease with increasing temperature. The influence of hydrogen bonding on the solvent and internal reorganization energy of betaine-30 is considered, and the physical basis for nonlinear solvent response is discussed.     

N-甲基吡咯-2-甲醛激发态结构动力学及其溶剂效应的共振拉曼光谱和密度泛函理论研究

获取了覆盖N-甲基吡咯-2-甲醛(NMPCA)A-带和B-带电子吸收共7个激发波长的共振拉曼光谱,并结合含时密度泛函理论(TD-DFT)方法研究了的A-带和B-带电子激发和Franck-Condon区域结构动力学.TD-B3LYP/6-311++G(d,p)计算表明:A-带和B-带电子吸收的跃迁主体为π→π*.共振拉曼光谱可以指认为,11-13振动模式(A-带激发)或者7-11振动模式(B-带激发)的基频、倍频和组合频,其中C=O伸缩振动(ν7)、环的变形振动+N1-C6伸缩振动(ν17)、环的变形振动(ν21)和C6-N1-C2/C2-C3-C4不对称伸缩振动(ν14)占据了绝大部分.这表明NMPCA的Sπ激发态结构动力学主要沿C=O伸缩振动、环的变形振动和环上N1-C6伸缩振动等反应坐标展开.在同一溶剂的共振拉曼光谱中随激发波长由长变短,ν7与ν14的强度比呈现出由强变弱再变强的现象,这种变化规律被认为与Franck-Condon区域Sn/Sπ态混合或势能面交叉有关.溶剂对Sn/Sπ态混合或势能面交叉具有调控作用.     

Resonance Raman intensity analysis of the A band short-time photochemical dynamics of 4,5-ethylenedithio-1,3-dithiole-2-thione

Resonance Raman spectra (RRs) for 4,5-ethylenedithio-1,3-dithiole-2-thione (EDDT) were obtained with 397.9 and 416 nm excitation wavelengths, and density functional calculations were performed to elucidate the electronic transitions and the RRs of EDDT in chloroform solvent. The RRs indicate that the Franck-Condon region photodynamics have multidimensional character with nuclear motion predominantly along the C(4)═C(5) stretch and the C(4)═C(5) twist out-of-plane. Resonance Raman cross-sections of A-band absorption have been obtained for the vibrational modes of EDDT with its excitation frequencies spanning the 408 nm. Resonance Raman intensity analysis of the resulting RRs excitation profiles and absorption spectrum using a time-dependent wave packet formalism yields mode-specific nuclear displacement and vibrational reorganizational energies. The intensity analysis results for EDDT were compared to previously reported results for dimethyl 1,3-dithiole-2-thione-4,5-dicarboxylate (DDTD), which shows that the additional six-member heterocycle of EDDT strongly affects the reorganizational energy and energy participation. The authors briefly discuss the differences and similarities of the spectra in terms of molecular symmetry and electron density.     

Calculated structural and electronic interactions of the ruthenium dye N3 with a titanium dioxide nanocrystal

Structural and electronic properties of a small anatase TiO2 nanocrystal sensitized by the ruthenium dye N3 (Ru(4,4'-dicarboxy-2,2'-bipyridine)2(NCS)2) have been investigated using density functional theory (DFT) with support from Hartree-Fock (HF) and time dependent DFT (TD-DFT) calculations. Significant structural adjustments of both the dye and the nanocrystal are predicted to be induced by the strain imposed by the simultaneous formation of multiple dye-surface bonds. Electronic properties of the combined dye-nanocrystal system have also been calculated, including information about interfacial orbital mixing and the lowest excited singlet states. Ultrafast photoinduced electron transfer processes across the dye-nanoparticle interface in dye-sensitized solar cells are finally discussed in view of estimated electronic coupling strengths. The calculations predict injection times on the order of 10 fs for MLCT excitations to the ligand pi* levels that interact most strongly with the TiO2 conduction band, and an order of magnitude increase in the injection times for excitations to dye levels with poor spatial or energetic overlaps with the substrate conduction band.     

Theory of photoinduced heterogeneous electron transfer

We consider electron injection into the conduction band of a semiconductor, from an electronically excited state of a dye molecule, adsorbed on its surface. For arbitrary width of the conduction band, the survival probability of the excited state can be calculated using a Green's-function approach. We show that the existence of a split-off state can play an important role in the total injection probability. In the wide band limit, the survival probability decays exponentially, but for finite band widths it does not. We further investigate the effect of vibrations on the process. A Green's operator technique may be used to solve this too exactly. We show that the problem may be reduced to a non-Hermitian eigenvalue problem for the vibrational states alone. Exact results can be obtained for arbitrary bandwidth and for a few vibrational degrees of freedom. In the wide band limit, the dynamics is particularly simple and we find that (1) the survival probability of the excited state is unchanged by the inclusion of vibrational motion, but (2) each vibrational state now has a finite lifetime. Numerical results are presented for the effects of reorganization energy, energy of the injecting level, and the variation of the matrix element for the electron injection, on the survival probability of the electron in the excited state. As an illustration of the approach, we also present results of numerical calculation of the absorption spectrum of perylene adsorbed on TiO(2) and compare it with experimental results.     

Raman under nitrogen. The high-resolution Raman spectroscopy of crystalline uranocene, thorocene, and ferrocene

The utility of recording Raman spectroscopy under liquid nitrogen, a technique we call Raman under nitrogen (RUN), is demonstrated for ferrocene, uranocene, and thorocene. Using RUN, low-temperature (liquid nitrogen cooled) Raman spectra for these compounds exhibit higher resolution than previous studies, and new vibrational features are reported. The first Raman spectra of crystalline uranocene at 77 K are reported using excitation from argon (5145 A) and krypton (6764 A) ion lasers. The spectra obtained showed bands corresponding to vibrational transitions at 212, 236, 259, 379, 753, 897, 1500, and 3042 cm(-1), assigned to ring-metal-ring stretching, ring-metal tilting, out-of-plane CCC bending, in-plane CCC bending, ring-breathing, C-H bending, CC stretching and CH stretching, respectively. The assigned vibrational bands are compared to those of uranocene in THF, (COT)2-, and thorocene. All vibrational frequencies of the ligands, except the 259 cm(-1) out-of-plane CCC bending mode, were found to increase upon coordination. A broad, polarizable band centered about approximately 460 cm(-1) was also observed. The 460 cm(-1) band is greatly enhanced relative to the vibrational Raman transitions with excitations from the krypton ion laser, which is indicative of an electronic resonance Raman process as has been shown previously. The electronic resonance Raman band is observed to split into three distinct bands at 450, 461, and 474 cm(-1) with 6764 A excitation. Relativistic density functional theory is used to provide theoretical interpretations of the measured spectra.     

尿嘧啶和5-氯尿嘧啶1S0→1S2跃迁动态结构的共振拉曼光谱

采用含时量子波包理论的简单模型对5-氯尿嘧啶和尿嘧啶的共振拉曼光谱开展了强度分析拟合, 获得了1(π, π*)激发态的几何结构变化动态特征. 结果表明, 尿嘧啶1S0→1S2跃迁的动态结构特征因5-位氯原子取代而改变. 5-氯尿嘧啶的动态结构特征主要沿C5=C6伸缩振动+C6H12 弯曲振动和N3H9/N1H7弯曲振动+N1C6伸缩振动反应坐标展开, 而尿嘧啶的动态结构特征主要沿嘧啶环的伸缩振动+C5H11/C6H12/N1H7弯曲振动和C4=O10伸缩振动反应坐标展开. π和π*轨道中氯原子的pz电子参与嘧啶环的p-π共轭作用导致了在1(π, π*)激发态上5-氯尿嘧啶的振动重组能更多地配分给嘧啶环的弯曲振动模式和C5=C6伸缩振动模式. 尿嘧啶在甲醇中的激发态动态结构特征与在水中的基本一致, 但波包沿C5H11/C6H12/N1H7弯曲振动+N1C6伸缩振动(υ12)和环呼吸振动(υ17)反应坐标的运动明显增强.