Raman Spectroscopy of Formamidinium-Based Lead Mixed-Halide Perovskite Bulk Crystals.

In recent years, there has been an impressively fast technological progress in the development of highly efficient lead halide perovskite solar cells. Nonetheless, the stability of perovskite films and associated solar cells remains a source of uncertainty and necessitates sophisticated characterization techniques. Here, we report low- to mid-frequency resonant Raman spectra of formamidinium-based lead mixed-halide perovskites. The assignment of the different Raman lines in the measured spectra is assisted by DFT simulations of the Raman spectra of suitable periodic model systems. An important result of this work is that both experiment and theory point to an increase of the stability of the perovskite structure with increasing chloride doping concentration. In the Raman spectra, this is reflected by the appearance of new lines due to the formation of hydrogen bonds. Thus, higher chloride doping results in less torsional motion and lower asymmetric bending contributing to higher stability. This study yields a solid basis for the interpretation of the Raman spectra of formamidinium-based mixed-halide perovskites, furthering the understanding of the properties of these materials, which is essential for their full exploitation in solar cells.

Decreasing toxicity and increasing photoconversion efficiency by Sn-substitution of Pb in 5-ammonium valeric acid-based two-dimensional hybrid perovskite materials.

The toxicity of Pb in halide-based hybrid perovskite materials stands in the way of their more extensive use, despite their excellent optical properties, high stability and very good photoconversion efficiency. The presented work focuses on addressing the toxicity issues in 2D perovskites. We use 5-ammonium valeric acid (AVA) as an organic spacer and partially or completely eliminate Pb by Sn and apply first principles-based density functional theory (DFT) calculations to determine the properties of these systems. Structural insights are gained, which predict the major changes in the inorganic framework including the metal-halide bond length and the bridging angle between two octahedral configurations. The replacement of Pb by Sn leads to a drastic reduction of the electronic band gap from 1.84 to 1.04 eV. Increasing the Sn content results in Sn-I bonds being stronger than the Pb-I bonds, which entails strong s-p coupling. The calculated effective masses of excitons decrease by up to ∼23% in the case of lead-free perovskites, which can be attributed to the more dispersive band edges due to stronger s-p coupling. The reduction of the effective masses of the charge carriers and the electronic band gap results in high electrical conductivity for the AVA2(MA)Sn2I7 2D perovskite structure. The three structures compared, where AVA2(MA)XI7 (X = Pb2, PbSn, Sn2) exhibit excellent thermoelectric power factors, which suggests promising applications for heat energy conversion. Moving toward lead-free 2D perovskites, the real part of the dielectric constants enhances, which may limit the radiative recombination of charge carriers. Furthermore, reducing the bandgap values by the substitution of Sn results in a red-shift in the edge of the absorption coefficients. Using the spectroscopic limited maximum efficiency (SLME) model, the best efficiencies of 32.20 and 30.08% are achieved for the AVA2(MA)PbSnI7 and AVA2(MA)Sn2I7 structures. The comparison of all three structures demonstrates that lead-free 2D perovskites are very good candidates for highly efficient solar energy conversion.

Dependence of CC stretching wavenumber on polyene length in degraded polyvinyl chloride: a comparative empirical, classical mechanics, and DFT study.

Mathematically describing the length-dependence of vibrational fingerprints of polyenes is challenging, yet crucial in understanding and predicting polyene-associated molecular properties of industrially-important and vital substances. To this end, we develop an analytical relationship between the wavenumbers ν∼C=C of the Raman-active CC stretching mode in polyene sequences (CHCH)n and the polyene length (n) using classical mechanics laws. Noteworthy, this relationship is derived from Newton's equations instead of regression approximations and validated against experimental data for degraded polyvinyl chloride (PVC), t-butyl end-capped all-trans polyenes, ß-carotenes, and carotenoids. Furthermore, given this fundamental tool, we carefully re-examined or validated the up-to-now applied empirical tools; we find that: (i) A phenomenological exponential regression function ν~C=C=1461+151.2×exp-0.07808n proves fairly suitable for describing polyenes with lengths below 24 in degraded PVC. (ii) The derived analytical relationship agrees more closely with a long-established reciprocal-length regression function ν~C=C=1459+720/n+1 for describing carotenoids. Moreover, extensive DFT calculation results on all-trans polyenes H(CHCH)nH (n = 3-30) and polyenes end-capped with terminal vinyl chloride oligomers agree with experiment for shorter polyenes and are similar, showing that complicated calculations of ν∼C=C for infinite degraded PVC chains reduce to the calculations on finite polyene sequences. Noteworthy, unlike other polyene length-determination tools, the proposed analytical polyene length-determination based on intrinsic physical properties could well prove to be an even more versatile tool, as it comes with the added potential for determining or correcting the elasticity constants of carbon bonds in polyene chains.

Hybrid Structure of Ionic Liquid and TiO2 Nanoclusters for Efficient Hydrogen Evolution Reaction.

Hydrogen energy has received significant attention in the renewable energy sector due to its high energy density and environmentally friendly nature. For the efficient hydrogen generation from water, the hydrogen evolution reaction (HER) has to be optimized, which requires a highly efficient electrocatalyst. In this work, a hybrid structure of the ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (C2mim TfO) and (TiO2)n nanoclusters with n = 2-12 has been investigated in the pursuit of new catalyst materials for effective HER. We have employed state-of-the-art density functional theory (DFT) computations to depict the HER catalytic performance of IL/(TiO2)n hybrid systems through Gibbs free energy (ΔG) and an exchange-current-based "volcano" plot. We have explored the effect of the TiO2 nanoclusters on the structural and electronic characteristics of the IL, calculating the adsorption energy, the energies of the highest occupied (HOMO) and lowest unoccupied molecular orbitals (LUMO), the HOMO-LUMO band gap Eg, and the work function ϕ. The variation in size of the TiO2 nanocluster in the IL/(TiO2)n hybrid system was found to have a significant influence on the electronic properties. The obtained results suggest that the ΔG of the hydrogen adsorption is remarkably close to the ideal value (0 eV) for the IL/(TiO2)5 system, which also reflects from the volcano plot, suggesting that this complex is the best HER catalyst among the studied systems; it might be even better than the traditional Pt-based catalyst. Thus, the present work suggests ways for the experimental realization of low-cost and multifunctional IL-based hybrid catalysts for clean and renewable hydrogen energy production.

Raman spectroscopic detection of polyene-length distribution for high-sensitivity monitoring of photo- and thermal degradation of polyvinylchloride.

The degradation of the ubiquitous polyvinylchloride (PVC) material under the influence of various factors is known to result commonly in polyene formation. Such polyene defects occur in the form of conjugated aliphatic chains with different lengths and contents, and their sensitive and length-specific monitoring is important for the assessment of PVC degradation. Here, we report on the resonance-enhanced Raman signatures of polyene sequences of varying lengths in photo- and thermally degraded PVC films. The lengths of polyene segments have been estimated based on their selectively enhanced and spectrally resolved contributions to the Raman bands assigned to the stretching vibrations of conjugated double carbon bonds. Using deconvolution analysis of a characteristic Raman band of polyenes, we especially demonstrate that the spectral signatures of polyene segments corresponding to other various electronic resonances contribute to the Raman spectral envelope observed at a given resonant excitation. In most cases, we observe an asymmetric band profile, indicating an asymmetric length distribution of polyene defects formed in PVC films upon a mild degradation extent less than 1% mass loss. We also demonstrate that the wavenumber (ν1) of the stretching vibrations of single carbon bonds in the polyene sequences of degraded PVC is inversely related to the number (n) of double carbon bonds by an empirical equation n=476·cm-1/ν1-1082·cm-1. To the best of our knowledge, while considering different laser excitations spanning the range of possible electronic resonances from blue to near-infrared for Raman investigations, the present work includes (i) the first Raman spectral deconvolution study for the 532.0 nm excitation wavelength used in most portable Raman probes nowadays and (ii) the screening of polyene defects also beyond the red edge of the visible spectrum and the evidence of a resonance-enhanced polyene signal at 647.1 nm. Important new information has been obtained about polyene lengths and spectral distribution for PVC, whose critical physical properties ranging from flexibility to electrical resistance are severely affected by polyene formation.

Nature of the different emissive states and strong exciton-phonon couplings in quasi-two-dimensional perovskites derived from phase-modulated two-photon micro-photoluminescence spectroscopy.

Quasi two-dimensional perovskites have attracted great attention for applications in light-emitting devices and photovoltaics due to their robustness and tunable highly efficient photoluminescence (PL). However, the mechanism of intrinsic PL in these materials is still not fully understood. In this work, we have analysed the nature of the different emissive states and the impact of temperature on the emissions in quasi two-dimensional methyl ammonium lead bromide perovskite (q-MPB) and cesium lead bromide perovskite (q-CPB). We have used spatially resolved phase-modulated two-photon photoluminescence (2PPL) and temperature-dependent 2PPL to characterize the emissions. Our results show that at room temperature, the PL from q-MPB is due to the recombination of excitons and free carriers while the PL from q-CPB is due to the recombination of excitons only. Temperature-dependent measurements show that in both materials the linewidth broadening is due to the interactions between the excitons and optical phonons at high temperatures. Comparing the characteristics of the emissions in the two systems, we conclude that q-CPB is better suited for light emitting devices. With a further optimization to reduce the impact on the environment, q-CPB-based LEDs could perform as well as OLEDs.

Effect of static external electric field on bulk and interfaces in organic solar cell systems: A density-functional-theory-based study.

In this work, a detailed comparison of optical and electronic properties in bulk and interfaces of well-known organic semiconductor systems in presence of an external electric field is reported. We have used density functional theory (DFT) to model organic solar cell systems. The study promotes a deeper understanding of the connection between the chemical structures and the optical and electronic properties in the well-known organic solar cell systems based on thiophene and fullerene polymers. We have performed a vibration-mode analysis by simulating Raman spectra in presence of external electric fields. Time-dependent DFT has been used to investigate the effect of an external electric field on excited state properties. The charge-transfer rate controlled by the external electric field has been quantitatively extracted using the simulated excited state dipole moment, Gibbs free energy, and Marcus theory. Our results provide a detailed characterization of the effect of the external electric field on the neat polymers (bulk) and on the donor-acceptor heterojunctions (interfaces) in organic solar cell systems. This theoretical approach not only helps to understand the effect of an external field on bulk and interfaces in organic semiconductors, but it also supports the design of novel devices.

Impact of alkyl chain length and water on the structure and properties of 1-alkyl-3-methylimidazolium chloride ionic liquids.

The influence of the length of the alkyl chain and water molecules on the hydrogen-bond interaction of the chloride anion and imidazolium-based cation of the ionic liquid (IL) Cnmim Cl (where n = 2, 4, 6, 8, and 10) was investigated by combining attenuated total internal reflection infrared (ATR-IR) spectroscopy and density functional theory (DFT) calculations. Here, for the first time, the conformational isomerism of the alkyl chain of Cnmim Cl (n = 2, 4, 6, 8, and 10) is identified by marker IR bands. The IR peak at 1470 cm-1 related to the alkyl chain vibration exhibits a significant perturbation in its intensity and further shows a red shift upon increasing alkyl chain length. This indeed might be a marker IR band for conformational isomerism and also an indication of the interaction of the alkyl chain with the chloride anion. Further, in the C-H vibration region of the IR spectra, a significant variation of the IR intensities was observed for the νs(CH2) and νas(CH2-CH3) modes at 2931 and 2976 cm-1, respectively. These bands can be considered as further markers for conformational isomerism of the alkyl chain. Moreover, the peak at 2976 cm-1 assigned to an alkyl chain vibration reveals the maximum red shift of 20 cm-1 for n = 10, which suggests charge redistribution among ion-pairs as a result of the alkyl chain variations. Noticeably, the C2-H vibration does not show any significant change of its wavenumber position, suggesting that the alkyl chain length does not interfere with the hydrogen bond interaction between C2-H and the Cl anion. This was also evident from the DFT-calculated bond strength between C2-H and Cl, which remains unchanged upon varying the alkyl chain length. In aqueous solutions, blue shifts of the v(C2-H) band by +65, +60, +67, +62 and +62 cm-1 for Cnmim Cl (n = 2, 4, 6, 8, and 10) are observed, respectively. These results point to a weakening of the hydrogen bond between cation and anion, which is also supported and validated by results of the solvent (water) effect obtained using the polarized continuum model (PCM) of the DFT calculations.

Insights into ultrafast charge-pair dynamics in P3HT:PCBM devices under the influence of static electric fields.

Polymer-fullerene blends based on poly(3-hexylthiophene-2,5-diyl) (P3HT) and phenyl-C61-butyric-acid methyl ester (PCBM) have been extensively studied as promising bulk heterojunction materials for organic semiconductor devices with improved performance. In these donor-acceptor systems where the bulk morphology plays a crucial role, the generation and subsequent decay mechanisms of photoexcitation species are still not completely understood. In this work, we use femtosecond transient absorption spectroscopy to investigate P3HT:PCBM diodes under the influence of applied static electric fields in comparison to P3HT:PCBM thin films. At the same time, we try to present a detailed overview about work already done on these donor-acceptor systems. The excited state dynamics obtained at 638 nm from P3HT:PCBM thin films are found to be similar to those observed earlier in neat P3HT films, while those obtained in the P3HT:PCBM devices are affected by field-induced exciton dissociation, resulting not only in comparatively slower decay dynamics, but also in bimolecular deactivation processes. External electric fields are expected to enhance charge generation in the investigated P3HT:PCBM devices by dissociating excitons and loosely bound intermediate species like polaron pairs (PPs) and charge transfer (CT) excitons, which can already dissociate only due to the intrinsic fields at the donor-acceptor interfaces. Our results clearly establish the formation of PP-like transient species different from CT excitons in the P3HT:PCBM devices as a result of a field-induced diffusion-controlled exciton dissociation process. We find that the loosely bound transient species formed in this way also are reduced in part via a bimolecular annihilation process resulting in charge loss in typical donor-acceptor P3HT:PCBM bulk heterojunction semiconductor devices, which is a rather interesting finding important for a better understanding of the performance of these devices.

Ultrafast polaron-pair dynamics in a poly(3-hexylthiophene-2,5-diyl) device influenced by a static electric field: insights into electric-field-related charge loss.

The generation and decay mechanisms of polaron pairs in organic semiconductor-based optoelectronic devices under operational conditions are relevant for a better understanding of photophysical processes affecting the device performance, since the possible occurrence of a polaron pair introduces an intermediate step in exciton dissociation into fully separated charge carriers. The role played by static electric fields in polaron-pair dynamics is important but poorly understood or not investigated in detail. In this work, insights into the polaron-pair dynamics in neat poly(3-hexylthiophene-2,5-diyl) (P3HT) thin films and P3HT films sandwiched between electrical contacts with an applied external static electric field are probed using femtosecond pump-probe transient absorption spectroscopy. Asymmetric contacts result in P3HT devices with application-related diode characteristics. Consistent with the electric field-induced dissociation of oppositely charged species, we show that polaron-pair dissociation into charge carriers occurs in the P3HT device more significantly with increasing reverse bias, and that this process follows an initial instantaneous polaron-pair photoabsorption quenching due to a pronounced immediate loss of primary photoexcitation species (hot excitons). Furthermore, we show that the net-electric field present in the P3HT diode (including built-in-potential at 0 V bias) results in a more complex dynamics with new findings as compared to the neat-P3HT thin film case. Indeed, besides polaron pairs directly originating from hot excitons, we experimentally observe polaron-pair formation during exciton dissociation via a field-mediated generation process, resulting in a slower contribution to the overall decay dynamics. Moreover, unlike in the external electric field-free P3HT film, bimolecular annihilation processes clearly appear as an additional loss channel when a field is applied and hence have an impact on carrier generation performance in a working device.

Peroxo-Cerium(IV)-Containing Polyoxometalates: [CeIV6(O2)9(GeW10O37)3]24-, a Recyclable Homogeneous Oxidation Catalyst.

The class of peroxo-cerium-containing polyoxometalates has been discovered via the synthesis of the 9-peroxo-6-cerium(IV)-containing 30-tungsto-3-germanate, [CeIV6(O2)9(GeW10O37)3]24- (1). Polyanion 1 consists of a cyclic [Ce6(O2)9]6+ assembly that is stabilized by three dilacunary [GeW10O37]10- Keggin fragments. The title polyanion 1 is solution-stable, on the basis of 183W nuclear magnetic resonance, and was shown to act as a recyclable homogeneous catalyst for the selective, microwave-activated sulfoxidation of the model substrate methionine to the sulfoxide in the absence and to the sulfone in the presence of hydrogen peroxide. Solution and solid-state Raman as well as solid-state infrared studies of 1 demonstrated the complete loss (and regain) of the nine peroxo groups in situ during the catalytic cycle, suggesting that the peroxo-free {Ce6(GeW10)3} skeleton remains most likely intact during the catalytic cycle. Solid-state X-ray photoelectron spectroscopy measurements showed that peroxo loss is accompanied by reduction of the cerium ions from +4 to +3, which is fully reversible. Density functional theory calculations are in complete agreement with all of these observations and furthermore suggest that the reduction of the six cerium(IV) ions is accompanied by the formation of molecular dioxygen.

Impact of Size and Electronegativity of Halide Anions on Hydrogen Bonds and Properties of 1-Ethyl-3-methylimidazolium-Based Ionic Liquids.

The effect of the anion size and electronegativity of halide-based anions (Cl-, Br-, I-, and BF4-) on the interionic interaction in 1-ethyl-3-methylimidazolium-based ionic liquids (ILs) C2mim X (X = Cl, Br, I, and BF4) is studied by a combined approach of experiments (Raman, IR, UV-vis spectroscopy) and quantum chemical calculations. The fingerprint region of the Raman spectra of these C2mim X ion-pairs provides evidence of the presence of the conformational isomerism in the alkyl chain of the C2mim+ cation. The Raman and IR bands of the imidazolium C2-H stretch vibration for C2mim X (X = Cl, Br, I, and BF4) were noticeably blue-shifted with the systematic change in size of anions and the electronegativity. The observed blue shift in the C2-H stretch vibration follows the order C2mim BF4 > C2mim I > C2mim Br > C2mim Cl, which essentially indicates the strong hydrogen bonding in the C2mim Cl ion-pair. DFT calculations predict at least four configurations for the cation-anion interaction. On the basis of relative optimized energies and basis-set-superposition-error (BSSE) corrected binding energies for all ion-pair configurations, the most active site for the anion interaction was found at the C2H position of the cation. Besides information about the C2H position, our DFT results give insights into the anion interaction with the ethyl and methyl chain of the cation, which was also confirmed experimentally [ Chem. Commun. 2015 , 51 , 3193 ]. The anion interaction at the C2H site of the cation favors a planar geometry in C2mim X for X = Cl, Br, and I; however, for BF4, the system prefers a nonplanar geometry where the anion is located over the imidazolium ring. TD-DFT results were used to analyze the observed UV-vis absorption spectra in a more adequate way giving insights into the electronic structure of the ILs. Overall, a reasonable correlation between the observed and the DFT-predicted results is established.

Interplay of Different Moieties in the Binary System 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate/Water Studied by Raman Spectroscopy and Density Functional Theory Calculations.

The present work reports new insights into specific interactions in aqueous solutions of the ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (C2mimTfO). A systematic investigation based on a combination of Raman spectroscopy and density functional theory (DFT) calculations shows evidence of self-encapsulation of the ionic moiety. Raman spectroscopy reveals preferred interactions between water molecules and the TfO- anions. The comparison of the experimental results with dispersion-corrected DFT calculations, which yield the predictions of the possible conformers of the cation-water, anion-water, and cation-anion-water structures, strongly supports the hypotheses of site-selective IL/water interactions. The obtained results allow for a detailed discussion of the nature and strength of the molecular interactions. It is shown that the TfO- anion establishes a preferred interaction with water, whereas the vibrational band at 3118 cm-1 for C-H motion at the C(2) position, the most acidic site for cation and anion interaction, does not indicate any specific energy shift, when adding water to the IL. This finding gives evidence for a self-protective microstructure of the molecules of C2mimTfO in an aqueous environment. In contrast to other ILs reported in the literature, there is no evidence of an increasing cation-anion distance in the IL ion-pair when increasing the water content. Instead, the C2mimTfO molecules undergo a perfect rearrangement, allowing interactions at other molecular sites with higher selectivity. A direct exposure to water at the cation-anion interacting site (C(2) position) is avoided. Ultimately, we show that clusters of ion-pair dimers solvated with water exhibit a more stable geometry compared to the hydrated single ion-pairs, and our calculations correctly reproduce the experimental findings.

Well-controlled in-situ growth of 2D WO3 rectangular sheets on reduced graphene oxide with strong photocatalytic and antibacterial properties.

Finding the materials, which help to control the water pollution caused by organic and bacterial pollutants is one of the challenging tasks for the scientific community. 2D sheets of WO3 and composite of WO3 and reduced graphene oxide (rGO) have been synthesized in a well-controlled way using a hydrothermal method. The as synthesized 2D sheet of WO3 and rGO-WO3 composite were characterized by various techniques. The 2D sheets of WO3 and rGO-WO3 composite are efficiently utilized for the photocatalytic degradation of methylene blue (MB) and Rhodamine B (RhB) dyes under sunlight. The rGO-WO3 composite reveals excellent photocatalytic degradation of RhB dye by degrading it upto 85% under sunlight. However, the MB dye was degraded by 32%. The greater degradation of RhB dye was explained in terms of the molecular electrostatic potential. We found that RhB has a more positive potential compared to MB dye where O2- and OH̊ radicals interact more strongly, resulting in a greater degradation of the RhB dye. The antibacterial activity of the 2D sheets of WO3 and rGO-WO3composite was also investigated on gram positive (B. subtilis) and gram negative (P. aeroginosa) microbes for the first time.

Influence of the alkyl side-chain length on the ultrafast vibrational dynamics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (CnmimNTf2) ionic liquids.

Probing the vibrational dynamics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (CnmimNTf2) ionic liquids (ILs) using femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) has indicated the ultrafast vibrational energy transfer between counter ions which is governed by interionic interactions and facilitated by hydrogen bonds. In this study, fs-CARS is used to investigate the ultrafast dynamics of the vibrational modes of the CnmimNTf2 ILs with n = 6, 8, 10, and 12 in a spectral region, which involves the imidazolium ring and the alkyl side-chain vibrations. The vibrational Raman modes with wavenumbers around 1418 cm-1 are excited through the CARS process and the ultrafast time evolution of the consequently excited vibrational modes is monitored. The investigation of the life times of the fs-CARS transient signals indicates that the time scale of the dynamics becomes much faster when the alkyl side-chain length of the CnmimNTf2 is longer than n = 8. This observation suggests an increase in the hydrogen bonding interactions due to the nano-structuring of the ionic liquids, which became evident with an increasing length of the alkyl side-chain. This behavior is also found in molecular dynamics simulations. There, an increase of the oxygen density around the C(2)-H moiety of the imidazolium ring, which is the predominant site for hydrogen bond formation, is observed. In other words, the longer the alkyl side-chain, the more reorganization of the ionic liquid into polar and non-polar domains occurs and the higher the probability of finding interionic hydrogen bonds at the C(2)-H position becomes.

Molecular Structure and Interactions in the Ionic Liquid 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate.

Quantum chemical theory (DFT and MP2) and vibrational spectroscopy (ATR-IR and Raman) were employed to investigate the electronic structure and molecular interactions in the room-temperature ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. Various possible conformers of a cation-anion pair based on their molecular interactions were simulated in the gas phase. All the different theoretical (MP2, B3LYP, and the dispersion-corrected wB97XD) methods assume the same ion-pair conformation for the lowest energy state. Basis set superimpose error (BSSE) correction was also introduced by using the counterpoise method. Strong C-H···O interactions between the most acidic hydrogen atom of the cation imidazole ring (C2H) and the oxygen atom of the anion were predicted where the anion is located at the top of (C2H). In this case, methyl and alkyl groups also interact with the anion in the form of a C-H···O hydrogen bond. Interestingly, the dispersion-corrected methodology neglects the C4/C5-H···O and C-H···F interaction in the ion-pair calculations. The theoretical results were compared with the experimental observations from Raman scattering and ATR-IR absorption spectroscopy, and the predictions of the molecular interactions in the vibrational spectra were discussed. The wavenumber shifts of the characteristic vibrations relative to the free cation and anion are explained by estimating the geometric parameters as well as the difference in the natural bond orbital (NBO) charge density.

One-step in situ synthesis of CeO2 nanoparticles grown on reduced graphene oxide as an excellent fluorescent and photocatalyst material under sunlight irradiation.

CeO2 nanoparticles (NPs) with average particle size of ∼17 nm were grown on graphene sheets by simply mixing cerium chloride as the Ce precursor with graphene oxide (GO) in distilled water and the simultaneous reduction of GO to reduced graphene oxide (rGO), followed by a one-step hydrothermal treatment at 150 °C. A unique blue to green tuneable luminescence was observed as a function of the excitation wavelength. With this method, significant applications of rGO-CeO2 nanocomposites in many optical devices could be realized. The photocatalytic activity of the as-synthesized CeO2 and rGO-CeO2 nanocomposite was investigated by monitoring the degradation of methylene blue (MB) dye under direct sunlight irradiation. The rGO-CeO2 nanocomposite exhibited excellent photocatalytic activity compared to CeO2 NPs by degrading 90% of the MB dye in 10 min irradiation under sunlight. This property of rGO-CeO2 nanocomposites was ascribed to the significant suppression of the recombination rate of photo-generated electron-hole pairs due to charge transfer between rGO sheets and CeO2 NPs and the smaller optical band-gap in the rGO-CeO2 nanocomposite.

Correction: One step in situ synthesis of CeO2 nanoparticles grown on reduced graphene oxide as an excellent fluorescent and photocatalyst material under sunlight irradiation.

Correction for 'One step in situ synthesis of CeO2 nanoparticles grown on reduced graphene oxide as an excellent fluorescent and photocatalyst material under sunlight irradiation' by Animesh Kumar Ojha et al., Phys. Chem. Chem. Phys., 2015, DOI: .

Combined Labelled and Label-free SERS Probes for Triplex Three-dimensional Cellular Imaging.

Cells are complex chemical systems, where the molecular composition at different cellular locations and specific intracellular chemical interactions determine the biological function. An in-situ nondestructive characterization of the complicated chemical processes (like e.g. apoptosis) is the goal of our study. Here, we present the results of simultaneous and three-dimensional imaging of double organelles (nucleus and membrane) in single HeLa cells by means of either labelled or label-free surface-enhanced Raman spectroscopy (SERS). This combination of imaging with and without labels is not possible when using fluorescence microscopy. The SERS technique is used for a stereoscopic description of the intrinsic chemical nature of nuclei and the precise localization of folate (FA) and luteinizing hormone-releasing hormone (LHRH) on the membrane under highly confocal conditions. We also report on the time-dependent changes of cell nuclei as well as membrane receptor proteins during apoptosis analyzed by statistical multivariate methods. The multiplex three-dimensional SERS imaging technique allows for both temporal (real time) and spatial (multiple organelles and molecules in three-dimensional space) live-cell imaging and therefore provides a new and attractive 2D/3D tracing method in biomedicine on subcellular level.

Ultrafast vibrational dynamics and energy transfer in imidazolium ionic liquids.

Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) is used as a probe for monitoring the vibrational dynamics of room temperature ionic liquids (ILs). The experiments are performed on a series of 1,3-dialkylimidazolium ILs containing the bis(trifluoromethylsulfonyl)imide [NTf2] anion. The effect of methylation of the cationic C2 position on the dephasing time is studied analyzing [NTf2]-ILs of 1-ethyl-3-methylimidazolium [EMIM], 1-ethyl-2,3-dimethylimidazolium [EMMIM], 1-butyl-3-methylimidazolium [BMIM], and 1-butyl-2,3-dimethylimidazolium [BMMIM]. Raman coherences are excited around ∼1400 cm(-1), and the vibrational dephasing of the modes in the fingerprint region is monitored as a function of time. The results indicate that vibrational energy transfer occurs governed by the interionic interactions. This is suggested by mode beating involving vibrations beyond the excitation spectrum as well as systematic differences in the temporal dephasing behavior. In contrast, the length of the cationic alkyl side chain has a negligible impact on the vibrational dynamics.