Hirendra N. Ghosh

Exciton Energy and Charge Transfer in Porphyrin Aggregate/Semiconductor (TiO2) Composites.

A porphyrin aggregate is reported that exhibits novel exciton state properties for light-harvesting applications. This porphyrin aggregate enables control of energy dissipation of coherent excited states by changing the self-assembly pattern. New exciton spectral features create a new route of energy transfer in this porphyrin aggregate. The kinetic model of exciton state decay is addressed in this Perspective by reporting steady-state and transient emission and absorption studies of porphyrin J- and H-aggregates. The porphyrin J-aggregate emerges with better spectral coverage and exciton dynamics, which are suitable for light-harvesting antenna functions. This motif is explored in a photosensitization study of TiO2 semiconductor materials. The transient absorption studies show that the J-aggregate improves the photoinduced charge separation at the porphyrin/TiO2 interface. The higher charge separation is attributed to exciton-coupled charge-transfer processes in porphyrin J-aggregate/TiO2 hybrid materials. It represents the potential of porphyrin aggregates in biomimetic artificial antenna activity.

Ultrafast Exciton Dynamics of J- and H-Aggregates of the Porphyrin-Catechol in Aqueous Solution

The aggregation behavior of 5,10,15-trisphenyl-20-(3,4-dihydroxy phenyl) porphyrin (L) in aqueous solution has been studied as a function of pH and concentration with the help of steady state absorption and emission spectroscopy. Our studies revealed that, for a particular concentration range, molecules of L undergo a reversible aggregation process and form two different aggregates at two different pH ranges, namely, J- and H-aggregates. We have monitored the excited state lifetimes of different aggregates by picosecond time-resolved emission spectroscopy and found that the emission lifetime of L reduces drastically with the formation of these aggregates. To study the dynamics associated with the excited state of both non-aggregated and aggregated (both J and H) porphyrins in an ultrafast time domain, we have carried out femtosecond transient absorption spectroscopy in the visible region following excitation of the respective samples at 400 nm. In addition to other de-excitation channels, another extra 100 fs (major) component for H-aggregates and 200 fs (major) component for J-aggregates has been observed and attributed to the exciton decay components of the respective aggregates.

Electron Trap to Electron Storage Center in Specially Aligned Mn-Doped CdSe d-Dot: A Step Forward in the Design of Higher Efficient Quantum-Dot Solar Cell

Specially aligned surface-accumulated Mn-doped CdSe (MnCdSe) quantum dots (QDs) have been synthesized to study the effect of dopant atom on charge-carrier dynamics in QD materials. EPR studies suggest that the (4)T1 state of Mn(2+) lies above the conduction band of CdSe, and as a result no Mn-luminescence was observed from MnCdSe. Femtosecond transient absorption studies suggest that Mn atom introduces structural defects in surface-doped CdSe, which acts as electron trap center in doped QD for the photoexcited electron. Bromo-pyrogallol red (Br-PGR) were found to form strong charge-trasfer complex with both CdSe and MnCdSe QDs. Charge separation in both the CdSe/Br-PGR and MnCdSe/Br-PGR composites was found to take place in three different pathways by transferring the photoexcited hole of CdSe/MnCdSe QDs to Br-PGR, electron injection from photoexcited Br-PGR to the QDs, and direct electron transfer from the HOMO of Br-PGR to the conduction band of both the QDs. Hole-transfer dynamics are found to be quite similar (∼1.1 to 1.3 ps) for both of the systems and found to be independent of Mn doping. However, charge recombination dynamics was found to be much slower in the MnCdSe/Br-PGR system as compared with that in the CdSe/Br-PGR system, which confirms that the Mn dopant act as the electron storage center. As a consequence, the MnCdSe/Br-PGR system can be used as a better super sensitizer in quantum-dot-sensitized solar cell to increase efficiency further.

Multiple-timescale photoreactivity of a model compound related to the active site of [FeFe]-hydrogenase.

Ultraviolet (UV) photolysis of (mu-S(CH 2) 3S)Fe 2(CO) 6 ( 1), a model compound of the Fe-hydrogenase enzyme system, has been carried out. When ultrafast UV-pump infrared (IR)-probe spectroscopy, steady-state Fourier transform IR spectroscopic methods, and density functional theory simulations are employed, it has been determined that irradiation of 1 in an alkane solution at 350 nm leads to the formation of two isomers of the 16-electron complex (mu-S(CH 2) 3S)Fe 2(CO) 5 within 50 ps with evidence of a weakly associated solvent adduct complex. 1 is subsequently recovered on timescales covering several minutes. These studies constitute the first attempt to study the photochemistry and reactivity of these enzyme active site models in solution following carbonyl ligand photolysis.

Efficient luminescence and photocatalytic behaviour in ultrafine TiO2 particles synthesized by arrested precipitation

We have demonstrated optical and photophysical properties of newly synthesized ultrasmall TiO2nanoparticles. The particles are synthesized by arrested precipitation method in trioctylphosphine oxide (TOPO) and benzophenone as the capping agent and also as solvent at high temperature in Ar atmosphere. High-resolution TEM and XRD measurements revealed that the particles are in the size range of 3.3–3.5 nm. Optical absorption spectra of these particles show large blue shift indicating a quantum confinement effect. The particles are highly luminescent, which is very unusual for an indirect band gap material. The emission quantum yield has been measured to be >2%. Again the photocatalytic activity of newly synthesized TiO2 particles was found to be much higher as compared to TiO2nanoparticles, indicating a better photocatalytic material arising due to size quantization.

Exciton-Coupled Charge-Transfer Dynamics in a Porphyrin J-Aggregate/TiO2 Complex

Exciton-coupled charge-transfer (CT) dynamics in TiO(2) nanoparticles (NP) sensitized with porphyrin J-aggregates has been studied by femtosecond time-resolved transient absorption spectroscopy. J-aggregates of 5,10,15-triphenyl-20-(3,4-dihydroxyphenyl) porphyrin (TPPcat) form CT complexes on TiO(2) NP surfaces. Catechol-mediated strong CT coupling between J-aggregate and TiO(2) NP facilitates interfacial exciton dissociation for electron injection into the conduction band of the TiO(2) nanoparticle in pulse width limited time (<80 fs). Here, the electron-transfer (<80 fs) process dominates over the intrinsic exciton-relaxation process (J-aggregates: ca. 200 fs) on account of exciton-coupled CT interaction. The parent hole on J-aggregates is delocalized through J-aggregate excitonic coherence. As a result, holes immobilized on J-aggregates are spatially less accessible to electrons injected into TiO(2) , and thus the back electron transfer (BET) process is slower than that of the monomer/TiO(2) system. The J-aggregate/porphyrin system shows exciton spectral and temporal properties for better charge separation in strongly coupled composite systems.

Extensive Reduction in Back Electron Transfer in Twisted Intramolecular Charge‐Transfer (TICT) Coumarin‐Dye‐Sensitized TiO2 Nanoparticles/Film: A Femtosecond Transient Absorption Study

We report the synthesis, characterization, and optical and electrochemical properties of two structurally similar coumarin dyes (C1 and C2). These dyes have been deployed as sensitizers in TiO2 nanoparticles and thin films, and the effect of molecular structure on interfacial electron-transfer dynamics has been studied. Steady-state optical absorption, emission, and time-resolved emission studies on both C1 and C2, varying the polarity of the solvent and the solution pH, suggest that both photoexcited dyes exist in a locally excited (LE) state in solvents of low polarity. In highly polar solvents, however, C1 exists in an intramolecular charge-transfer (ICT) state, whereas C2 exists in both ICT and twisted intramolecular charge-transfer (TICT) states, their populations depending on the degree of polarity of the solvent and the pH of the solution. We have employed femtosecond transient absorption spectroscopy to monitor the charge-transfer dynamics in C1- and C2-sensitized TiO2 nanoparticles and thin films. Electron injection has been confirmed by direct detection of electrons in the conduction band of TiO2 nanoparticles and of radical cations of the dyes in the visible and near-IR regions of the transient absorption spectra. Electron injection in both the C1/TiO2 and C2/TiO2 systems has been found to be pulse-width limited (<100 fs); however, back-electron-transfer (BET) dynamics has been found to be slower in the C2/TiO2 system than in the C1/TiO2 system. The involvement of TICT states in C2 is solely responsible for the higher electron injection yield as well as the slower BET process compared to those in the C1/TiO2 system. Further pH-dependent experiments on C1- and C2-sensitized TiO2 thin films have corroborated the participation of the TICT state in the slower BET process in the C2/TiO2 system.

On the role of hydrogen bonds in photoinduced electron-transfer dynamics between 9-fluorenone and amine solvents.

Using ultrafast fluorescence upconversion and mid-infrared spectroscopy, we explore the role of hydrogen bonds in the photoinduced electron transfer (ET) between 9-fluorenone (FLU) and the solvents trimethylamine (TEA) and dimethylamine (DEA). FLU shows hydrogen-bond dynamics in the methanol solvent upon photoexcitation, and similar effects may be anticipated when using DEA, whereas no hydrogen bonds can occur in TEA. Photoexcitation of the electron-acceptor dye molecule FLU with a 400 nm pump pulse induces ultrafast ET from the amine solvents, which is followed by 100 fs IR probe pulses as well as fluorescence upconversion, monitoring the time evolution of marker bands of the FLU S(1) state and the FLU radical anion, and an overtone band of the amine solvent, marking the transient generation of the amine radical cation. A comparison of the experimentally determined forward charge-separation and backward charge-recombination rates for the FLU-TEA and FLU-DEA reaction systems with the driving-force dependencies calculated for the forward and backward ET rates reveals that additional degrees of freedom determine the ET reaction dynamics for the FLU-DEA system. We suggest that hydrogen bonding between the DEA molecules plays a key role in this behaviour.

Super Sensitization: Grand Charge (Hole/Electron) Separation in ATC Dye Sensitized CdSe, CdSe/ZnS Type‐I, and CdSe/CdTe Type‐II Core–Shell Quantum Dots

Ultrafast charge-transfer dynamics has been demonstrated in CdSe quantum dots (QD), CdSe/ZnS type-I core-shell, and CdSe/CdTe type-II core-shell nanocrystals after sensitizing the QD materials by aurin tricarboxylic acid (ATC), in which CdSe QD and ATC form a charge-transfer complex. Energy level diagrams suggest that the conduction and valence band of CdSe lies below the LUMO and the HOMO level of ATC, respectively, thus signifying that the photoexcited hole in CdSe can be transferred to ATC and that photoexcited ATC can inject electrons into CdSe QD, which has been confirmed by steady state and time-resolved luminescence studies and also by femtosecond time-resolved absorption measurements. The effect of shell materials (for both type-I and type-II) on charge-transfer processes has been demonstrated. Electron injection in all the systems were measured to be <150 fs. However, the hole transfer time varied from 900 fs to 6 ps depending on the type of materials. The hole-transfer process was found to be most efficient in CdSe QD. On the other hand, it has been found to be facilitated in CdSe/CdTe type-II and retarded in CdSe/ZnS type-I core-shell materials. Interestingly, electron injection from photoexcited ATC to both CdSe/CdTe type-II and CdSe/ZnS type-I core-shell has been found to be more efficient as compared to pure CdSe QD. Our observation suggests the potential of quantum dot core-shell super sensitizers for developing more efficient quantum dot solar cells.

Charge separation, charge recombination and electron transfer reactions in solutions of fullerene-C60 and phenothiazines

Abstract C 60 forms weak charge transfer complexes with phenothiazine and methyl phenothiazine. Charge separation, charge recombination and ion dissociation reactions were investigated in the solution phase following excitation of the charge transfer band of the complexes with picosecond laser pulses. The formation of the triplet state of C 60 on charge recombination, and electron transfer reactions of the singlet and triplet states of C 60 with phenothiazine to give C 60 −· and cation radicals have been investigated. On longer timescales (> 1 μ s) back electron transfer between C 60 −· and cation radical takes place. The effect of solvent polarity was studied on the charge recombination and back electron transfer reactions.