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Spectroscopic studies were done to examine the protonation and excitation dynamics of green fluorescent protein (GFP), the electronic, resonance Raman. Substantial differences are observed between the resonance Raman spectra of GFP and the 4-hydroxybenzylidene-2,3-dimethyl-imidazolinone (HBDI).

The linear and nonlinear optical properties of macrocyclic trichromophore bundle (1) and a single chromophore standard are studied by ultraviolet (UV)-vis absorption, fluorescence, solvatochromic spectrometry and hyper-Rayleigh scattering (HRS). The hypsochromic shift and fluorescence quenching are consistent with the exciton theory and the enhanced solvatochromic shift is due to solvent mediation of electrostatic interactions among the chromophores in 1.

A single-molecule confocal microscopy study of electric-field poling in a chromophore-polymer composite material is presented. The observed single-molecule rational dynamics in the presence and absence of the electric field are analyzed to determine the change in rotational dynamics introduced by the presence of the poling field.

Single-molecule confocal microscopy studies of orientational distributions for luminophores isolated in potassium hydrogen pthalate (KAP) crystals are presented. Average orientations determined at the single-molecule level were in close agreement to ensemble-averaged measurements, and the chromophore orientational distributions were broader than anticipated, indicating that the crystals incorporate guest molecules in a range of orientations outside the measured ensemble average.

The excited-state reaction dynamics of nitrosyl chloride (CINO) are studied using absolute resonance Raman intensity analysis. The analysis presented demonstrates that the photoexcitation of solution-phase CINO results in a substantial evolution of the N-Cl stretch coordinate consistent with the dissociation of the N-Cl bond.

The photochemistry of nitrosyl chloride (ClNO) dissolvedin cyclohexane is investigated using ultrafast time-resolved infrared(TRIR) spectroscopy. Following 266 nm photolysis, the photochemistryis measured by following changes in optical density at frequenciesspanning the NO stretch fundamental transition. A photoinduceddepletion in optical density is observed consistent with the depletionof ground-state ClNO. The depletion in optical density remains constantout to ∼50 ps demonstrating that ClNO photodissociation isnot followed by recombination of the Cl and NO photofragments. Inaddition, no evidence for the formation of the ClON photoisomer isobserved. These results stand in contrast to previous studies in acetonitrilewhere ClNO photolysis is followed by geminate recombination of Cland NO, and by the production of ClON. These differences in ClNO photochemistryare proposed to arise from the population of different excited-statescaused by solvent dependence of the ground-state potential energysurface minimum along the Cl–N stretch coordinate. Solvent-dependentvibrational relaxation and differences in strength of the solventcage are also proposed to contribute to the solvent-dependent photochemistry.Finally, these results are placed in the context of recent modelsof ClNO photochemistry and role of this compound in tropospheric ozoneproduction. [ABSTRACT FROM AUTHOR]

The dependence of single-molecule photoluminescence intermittency (PI) or "blinking" on the local dielectric constant (ε) is examined for nile red (NR) in thin films of poly(vinylidene fluoride) (PVDF). In previous studies, variation of the local dielectric constant was accomplished by studying luminophores in chemically and structurally different hosts. In contrast, the NR/PVDF guest-host pair allows for the investigation of PI as a function of ε while keeping the chemical composition of both the luminophore and host unchanged. The solvatochromic properties of NR are used to measure the local ε, while fluctuations in NR emission intensity over time provide a measure of the PI. PVDF is an ideal host for this study because it provides submicron-sized dielectric domains that vary from nonpolar (ε ≈ 2) to very polar (ε ≈ 70). The results presented here demonstrate that the local dielectric environment can have a pronounced effect on PI. We find that the NR emissive events increase 5-fold with an increase in ε from 2.2 to 74. A complex dependence on ε is also observed for NR nonemissive event durations, initially increasing as ε increases from 2.2 to 3.4 but decreasing in duration with further increase in ε. The variation in emissive event durations with ε is reproduced using a photoinduced electron-transfer model involving electron transfer from NR to PVDF. In addition, an increase in NR photostability with an increase in ε is observed, suggesting that the dielectric environment plays an important role in defining the photostability of NR in PVDF.

The variation in dielectric constant is measured for thin films of poly(methyl methacrylate) (PMMA) and poly(vinylidene fluoride) (PVDF) using confocal fluorescence microscopy. Spatial variation in the local dielectric constant of the polymer films on the ~250 nm length scale is measured using the solvochromatic emission from incorporated nile red (NR) at "quasi-single molecule" (10(-7) M) and true single molecule (SM) concentrations (10(-9) M). Correlation of the NR fluorescence wavelength maximum with dielectric constant is used to transform images of NR's emission maxima to spatial variation in local dielectric constant. We demonstrate that the distributions of dielectric environments measured in the quasi- and true SM approaches are equivalent; however, the enhanced signal rates present in the quasi-SM approach result in this technique being more efficient. In addition, the quasi-SM technique reports directly on the continuous spatial variation in dielectric constant, information that is difficult to obtain in true SM studies. With regards to the polymers of interest, the results presented here demonstrate that a limited distribution of dielectric environments is present in PMMA; however, a broad distribution of environments exists in PVDF consistent with this polymer existing as a distribution of structural phases.

The role of proton transfer in the photoluminescence intermittency (PI) of single molecules of violamine R (VR) overgrown in potassium acid phthalate (KAP) crystals is evaluated in comparisons of protonated (KAP) and deuterated (DKAP) mixed crystals between 23 and 60 °C. The PI is analyzed by the construction of cumulative distribution functions that are statistically compared. We find that the on- and off-interval duration distributions change with isotopic substitution consistent with proton transfer contributing to the PI of VR. The on- and off-interval duration distributions have distinct temperature dependencies consistent with different mechanisms for dark state production and decay. Additional evidence for proton-transfer is provided by distributions of single molecule emission-energy maxima that reflect emission from protonated and deprotonated VR. A mechanism for the PI of KAP is presented, where the dark state is assigned to formation of the colorless, leuco form of VR, formed by proton transfer from VR to the KAP lattice, and decay of the dark state involves ring-opening promoted by proton transfer from KAP to VR. The distributed kinetics for dark-state production and decay are modeled using a log-normal distribution for the PI data in preference to a power-law previously assumed. A discussion of the log-normal distribution with regards to PI and proton transfer is presented.

Experimental and computational studies of the solvent dependence of the first molecular hyperpolarizability (β) for two donor-bridge-acceptor chromophores (CLD-1 and YLD156) are presented. Hyper-Rayleigh scattering (HRS) measurements are performed with 1907 nm excitation in a series of solvents with dielectric constants ranging from ~2 (toluene) to ~36 (acetonitrile). For both chromophores an approximately 2-fold increase in β is observed by HRS over this range of dielectric constants. Computational studies employing a polarized continuum model to represent the solvent are capable of reproducing this experimental result. The experimental and computational results are compared to the predictions of the widely employed two-state model (TSM) for β. Surprisingly, for the chromophores studied here the TSM predicts that β should decrease with increasing dielectric constant over the range investigated. The results presented here demonstrate that the TSM provides neither a quantitative nor qualitative description of the solvent dependence of β for CLD-1 and YLD156. The enhancement of β with increased dielectric constant suggests that modification of the dielectric surrounding the chromophore is one path by which the performance of nonlinear optical devices employing these chromophores may be significantly enhanced.

Identification of electronic intermolecular electrostatic interactions that can significantly enhance poling-induced order is important to the advancement of the field of organic electro-optics. Here, we demonstrate an example of such improvement achieved through exploitation of the interaction of coumarin pendant groups in chromophore-containing macromolecules. Acentric order enhancement is explained in terms of lattice-symmetry effects, where constraint of orientational degrees of freedom alters the relationship between centrosymmetric and acentric order. We demonstrate both experimentally and theoretically that lattice dimensionality can be defined using the relationship between centrosymmetric order and acentric order. Experimentally: Acentric order is determined by attenuated total reflection measurement of electro-optic activity coupled with hyper-Rayleigh scattering measurement of molecular first hyperpolarizability, and centrosymmetric order is determined by the variable angle polarization referenced absorption spectroscopy method. Theoretically: Order is determined from statistical mechanical models that predict the properties of soft condensed matter.

A macrocyclic trichromophore bundle 1 with parallel-aligned dipole moments has been synthesized to study the influence of aggregation and orientation of a nonlinear optical (NLO) chromophore on its optical properties. The linear and nonlinear optical properties of 1 and a single chromophore standard 2 have been studied by UV-vis absorption, fluorescence, solvatochromic spectrometry, and hyper-Rayleigh scattering (HRS). Reduced first-order hyperpolarizability beta, hypsochromic shift, enhanced solvatochromic shifts, and fluorescence quenching for individual chromophores were observed when 1 was compared with 2. Analysis of the data showed that the transition dipole moment changes only slightly when the chromophores are parallel aligned in the bundle architecture. However, the apparent hyperpolarizability of the individual chromophores decreased significantly by about 20%. The reduction in beta for the individual chromophores in 1 is largely due to the hypsochromic shift, i.e., excitation energy increase of the interband (charge-transfer) energy gap and the reduced difference between the ground-state and excited-state dipole moments. The hypsochromic shift and fluorescence quenching are consistent with exciton theory. Possible reasons for the enhanced solvatochromic shift are discussed.