Jahur A. Mondal

Ultrafast Dynamics of the Excited States of Curcumin in Solution

Dynamics of the excited singlet (S(1)) state of curcumin has been investigated in a wide varieties of solvents using subpicosecond time-resolved fluorescence and absorption spectroscopic techniques. As a consequence of extra stability of the cis-enol conformer due to the presence of an intramolecular hydrogen bond, it is the major form existing in the ground-state and the excited-state processes described here has been attributed to this form. Steady-state absorption and fluorescence spectra suggest significant perturbation of the intramolecular hydrogen bond and the possibility of formation of intermolecular hydrogen-bonded complex with the hydrogen-bonding solvents. Both the time-resolved techniques used here reveal that solvation is the major process contributing to the relaxation dynamics of the S(1) state. Solvation dynamics in protic solvents is multimodal, and the linear correlation between the longest component of the solvation process and the longitudinal relaxation time of the solvent suggests the specific hydrogen-bonding interaction between the solute and the solvent. However, a good correlation between the experimentally determined average solvation time and that predicted by the dielectric continuum model in all kinds of solvents also suggests that the dielectric relaxation of the solvent is also an important contributor to the solvation process. The lifetime of the S(1) state is very short in nonpolar solvents (∼44 ps in 1,4-dioxane) because of efficient nonradiative deactivation of the S(1) state, which is an important consequence of the ultrafast excited-state intramolecular hydrogen transfer (ESIHT) reaction in the six-membered hydrogen-bonded chelate ring of the cis-enol form. However, it has not been possible to monitor the ESIHT reaction in real time because of the symmetrical structure of the molecule with respect to the hydrogen-bonded chelate ring. In polar solvents, dipole-dipole interaction perturbs the intramolecular hydrogen bond leading to the reduced efficiency of the nonradiative deactivation process. However, stretching vibration in the intermolecular hydrogen bonds formed in the hydrogen-bonding (both donating and accepting) solvents induces another efficient channel for the nonradiative relaxation of the S(1) state of curcumin.

Ultrafast twisting dynamics in the excited state of auramine.

Relaxation dynamics of the excited state of bis-[4-(dimethylamino)-phenyl] methaniminium chloride (Auramine) has been investigated using subpicosecond time-resolved absorption spectroscopic technique in both aprotic and alcoholic solvents. The locally excited (LE) state, formed following photoexcitation of Auramine using 400 nm light, undergoes intramolecular charge transfer (ICT) process, which is accompanied by the twisting of the dimethylanilino groups. Time evolution of the transient absorption-stimulated emission spectra as well as the wavelength dependence of the temporal dynamics investigated in each kind of solvents suggest that the relaxation process proceeds via the formation of at least two transient states (TS I and TS II), which are geometrical conformers and consecutively formed following the decay of the LE state. Twisting of the dimethylaniline groups are nearly barrierless processes, the rates of which show linear correlation both with the macroscopic or shear viscosities as well as the solvation times of the solvents. Time-dependent and fractional viscosity dependence of the relaxation rates of the LE and the TS I states in aprotic solvents suggest the multidimensionality of the reaction coordinate as well as reveal the viscoelastic property of the solvents. However, in normal alcohols, in addition to these two factors, activation energy of the solvent viscosity may be another important factor for the slower twisting dynamics of Auramine in alcohols. To explain the viscosity dependence of the decay time of the TS II state, which undergoes an efficient internal conversion process to the ground state, the possibility of occurrence of different mechanisms, such as, energy gap law, involvement of intramolecular high frequency modes, as well as the phenyl group twisting motion on a potential energy surface having a photochemical funnel, have been discussed. TDDFT method has been applied to obtain the optimized electronic structures of the transient states but it has been possible to obtain only that for the TS II state.

How ions affect the structure of water: a combined Raman spectroscopy and multivariate curve resolution study.

Raman spectroscopy in combination with multivariate curve resolution (Raman-MCR) is used to explore the interaction between water and various kosmotropic and chaotropic anions. Raman-MCR of aqueous Na-salt (NaI, NaBr, NaNO3, Na2SO4, and Na3PO4) solutions provides solute-correlated Raman spectra (SC-spectra) of water. The SC-spectra predominantly bear the vibrational characteristics of water in the hydration shell of anions, because Na(+)-cation has negligible effect on the OH stretch band of water. The SC-spectra for the chaotropic I(-), Br(-), and NO3(-) anions and even for the kosmotropic SO4(2-) anion resemble the Raman spectrum of isotopically diluted water (H2O/D2O = 1/19; v/v) whose OH stretch band is largely comprised by the response of vibrationally decoupled OH oscillators. On the other hand, the SC-spectrum for the kosmotropic PO4(3-) anion is quite similar to the Raman spectrum of H2O (bulk). Comparison of the peak positions of SC-spectra and the Raman spectrum of isotopically diluted water suggests that the hydrogen bond strength of water in the hydration shell of SO4(2-) is comparable to that of the isotopically diluted water, but that in the hydration shell of I(-), Br(-), and NO3(-) anions is weaker than that of the latter. Analysis of integrated area of component bands of the SC-spectra reveals ∼80% reduction of the delocalization of vibrational modes (intermolecular coupling and Fermi resonance) of water in the hydration shell of I(-), Br(-), NO3(-), and SO4(2-) anions. In the case of trivalent PO4(3-), the vibrational delocalization is presumably reduced and the corresponding decrease in spectral response at ∼3250 cm(-1) is compensated by the increased signal of strongly hydrogen bonded (but decoupled) water species in the hydration shell. The peak area-averaged wavenumber of the SC-spectrum increases as PO4(3-) < SO4(2-) < NO3(-) < Br(-) < I(-) and indeed suggests strong hydrogen bonding of water in the hydration shell of PO4(3-) anion.

Water in the hydration shell of halide ions has significantly reduced Fermi resonance and moderately enhanced Raman cross section in the OH stretch regions.

Water in the presence of electrolytes plays an important role in biological and industrial processes. The properties of water, such as the intermolecular coupling, Fermi resonance (FR), hydrogen-bonding, and Raman cross section were investigated by measuring the Raman spectra in the OD and OH stretch regions in presence of alkali halides (NaX; X = F, Cl, Br, I). It is observed that the changes in spectral characteristics by the addition of NaX in D2O are similar to those obtained by the addition of H2O in D2O. The spectral width decreases significantly by the addition of NaX in D2O (H2O) than that in the isotopically diluted water. Quantitative estimation, on the basis of integrated Raman intensity, revealed that the relative Raman cross section, σ(H)/σ(b) (σ(H) and σ(b) are the average Raman cross section of water in the first hydration shell of X(-) and in bulk, respectively), in D2O and H2O is higher than those in the respective isotopically diluted water. These results suggest that water in the hydration shell has reduced FR and intermolecular coupling compared to those in bulk. In the isotopically diluted water, the relative Raman cross section increases with increase in size of the halide ions (σ(H)/σ(b) = 0.6, 1.1, 1.5, and 1.9 for F(-), Cl(-), Br(-), and I(-), respectively), which is assignable to the enhancement of Raman cross section by charge transfer from halide ions to the hydrating water. Nevertheless, the experimentally determined σ(H)/σ(b) is lower than the calculated values obtained on the basis of the energy of the charge transfer state of water. The weak enhancement of σ(H)/σ(b) signifies that the charge transfer transition in the hydration shell of halide ions causes little change in the OD (OH) bond lengths of hydrating water.

On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions

The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) < bulk water < Cl(-) < I(-). It is believed that these structural perturbations influence the dynamics of coherent energy transfer and librational reorientation of water in the hydration shell of anions.

The Role of Hydrogen‐Bonding Interactions in the Ultrafast Relaxation Dynamics of the Excited States of 3‐ and 4‐Aminofluoren‐9‐ones

The dynamics of the excited states of 3- and 4-aminofluoren-9-ones (3AF and 4AF, respectively) are investigated in different kinds of solvents by using a subpicosecond time-resolved absorption spectroscopic technique. They undergo hydrogen-bonding interaction with protic solvents in both the ground and excited states. However, this interaction is more significant in the lowest excited singlet (S(1)) state because of its substantial intramolecular charge-transfer character. Significant differences in the spectroscopic characteristics and temporal dynamics of the S(1) states of 3AF and 4AF in aprotic and protic solvents reveal that the intermolecular hydrogen-bonding interaction between the S(1) state and protic solvents plays an important role in its relaxation process. Perfect linear correlation between the relaxation times of the S(1) state and the longitudinal relaxation times (tau(L)) of alcoholic solvents confirms the prediction regarding the solvation process via hydrogen-bond reorganization. In the case of weakly interacting systems, the relaxation process can be well described by a dipolar solvation-like process involving rotation of the OH groups of the alcoholic solvents, whereas in solvents having a strong hydrogen-bond-donating ability, for example, methanol and trifluoroethanol, it involves the conversion of the non-hydrogen-bonded form to the hydrogen-bonded complex of the S(1) state. Efficient radiationless deactivation of the S(1) state of the aminofluorenones by protic solvents is successfully explained by the energy-gap law, by using the energy of the fully solvated S(1) state determined from the time-resolved spectroscopic data.

Photoisomerization dynamics of N-1-methyl-2-(tolylazo) imidazole and the effect of complexation with Cu(II).

Azo-compounds containing an imidazole moiety have the potential to photoregulate biofunctions, such as gene-expression and enzymatic action. Photoinduced isomerization of the azo-backbone is the vital process for such applications, but the photoisomerization dynamics of azo-imidazole compounds has not been well explored. We investigated the photoisomerization dynamics of trans-N-1-methyl-2-(tolylazo) imidazole (trans-MTAI) using femtosecond transient absorption spectroscopy following photoexcitation to the S(2) state. Time evolution of the transient electronic spectra and the global analysis of the temporal profiles reveal a three state relaxation (S(2) → S(1) → S(0)) process in different kinds of solvents. The lifetime of the S(2) state is independent of the viscosity of solvent, whereas that of the S(1) state becomes longer with increasing solvent viscosity. This observation clearly indicates that the large amplitude motion that leads to the trans → cis isomerization occurs only in the S(1) state and relaxation of the S(2) state is not associated with the isomerization process. We have also investigated the excited state dynamics of [Cu(trans-MTAI)(2)]Cl(2) to examine the effect of complexation with the metal ion on the isomerization dynamics of trans-MTAI. It is observed that the photoinduced isomerization of the azo-backbone in trans-MTAI is completely inhibited upon complexation with Cu(II).

Ultrafast Dynamics of the Excited States of the Uranyl Ion in Solutions

We have investigated the relaxation dynamics of the higher excited states of the uranyl ion in aqueous and methanolic solutions following photoexcitation to the S(1)((1)Phi(g)) state using 400 nm light. Although the time-resolved spectra are significantly different in these two solvents, the temporal dynamics studied in the entire wavelength region clearly suggest the involvement of three excited state processes in both solvents. The S(1)((1)Phi(g)) state undergoes ultrafast intersystem crossing (tau(ISC) approximately <100 fs) to the higher vibrational levels of the T(2)((3)Delta(g)) state, followed by the intramolecular vibrational relaxation (IVR) process in the later electronic state (tau(IVR) approximately 0.85 and 1 ps in aqueous and methanolic solutions, respectively). Subsequently, the T(2)((3)Delta(g)) state undergoes an internal conversion (IC) process (tau(IC) approximately l.6 and 4.5 ps in aqueous and methanol solutions, respectively) to the long-lived T(1)((3)Phi(g)) state, which is responsible for the luminescent properties of the uranyl ion. In neat methanol, because of stronger interaction between the excited triplet, T(1)((3)Phi(g)), state and the solvent via solvent to uranyl charge transfer, the U(VI) ion undergoes partial reduction to U(V) and the energy level of this state possibly lies lower than that of (UO(2)(2+))*, which is the transient species existing in aqueous solution, and hence increasing the energy gap between the T(2) and T(1) states in methanol solution. These facts possibly explain different spectral characteristics of the transient species produced in methanol and aqueous solutions as well as the longer lifetime of the IC process in methanol solution.

Ultrafast Relaxation Dynamics of the Excited States of 1‐Amino‐ and 1‐(N,N‐Dimethylamino)‐fluoren‐9‐ones

The dynamics of the excited states of 1-aminofluoren-9-one (1AF) and 1-(N,N-dimethylamino)-fluoren-9-one (1DMAF) are investigated by using steady-state absorption and fluorescence as well as subpicosecond time-resolved absorption spectroscopic techniques. Following photoexcitation of 1AF, which exists in the intramolecular hydrogen-bonded form in aprotic solvents, the excited-state intramolecular proton-transfer reaction is the only relaxation process observed in the excited singlet (S(1)) state. However, in protic solvents, the intramolecular hydrogen bond is disrupted in the excited state and an intermolecular hydrogen bond is formed with the solvent leading to reorganization of the hydrogen-bond network structure of the solvent. The latter takes place in the timescale of the process of solvation dynamics. In the case of 1DMAF, the main relaxation pathway for the locally excited singlet, S(1)(LE), or S(1)(ICT) state is the configurational relaxation, via nearly barrierless twisting of the dimethylamino group to form the twisted intramolecular charge-transfer, S(1)(TICT), state. A crossing between the excited-state and ground-state potential energy curves is responsible for the fast, radiationless deactivation and nonemissive character of the S(1)(TICT) state in polar solvents, both aprotic and protic. However, in viscous but strong hydrogen-bond-donating solvents, such as ethylene glycol and glycerol, crossing between the potential energy surfaces for the ground electronic state and the hydrogen-bonded complex formed between the S(1)(TICT) state and the solvent is possibly avoided and the hydrogen-bonded complex is weakly emissive.

Femtosecond transient absorption studies in cadmium selenide nanocrystal thin films prepared by chemical bath deposition method

Dynamics of photo-excited carrier relaxation processes in cadmium selenide nanocrystal thin films prepared by chemical bath deposition method have been studied by nondegenerate femtosecond transient pump-probe spectroscopy. The carriers were generated by exciting at 400 nm laser light and monitored by several other wavelengths. The induced absorption followed by a fast bleach recovery observed near and above the bandgap indicates that the photo-excited carriers (electrons) are first trapped by the available traps and then the trapped electrons absorb the probe light to show a delayed absorption process. The transient decay kinetics was found to be multiexponential in nature. The short time constant, <1 picosecond, was attributed to the trapping of electrons by the surface and/or deep traps and the long time constant, ≥20 picoseconds, was due to the recombination of the trapped carriers. A very little difference in the relaxation processes was observed in the samples prepared at bath temperatures from 25°C to 60°C.