Quantitative Modeling of Electron Dynamics and the Effect of Diffusion in Photosensitized Semiconductor Nanocomposites.

Photosensitized semiconducting nanomaterials have received considerable attention because of their applications in photocatalytic and photoelectronic devices. In such systems, photoexcited electrons with sufficiently high energies can be injected into the conduction band (CB) of an adjacent semiconductor. These excited electrons are subjected to various physical processes that can lead to their annihilation before exercising their catalytic/electric functions, and the efficiency of the photosensitized functions depends on the quantity of CB electrons produced and how long they remain near the surface region of the semiconductor. The rise and decay of photoexcited electrons in the semiconductor CB can be probed with transient IR absorption (TA), which was first demonstrated by Lian and co-workers. Results from various laboratories have since revealed that electrons appear in the CB following the excitation of the photosensitizer in tens to hundreds of femtoseconds and that the decay of the CB electrons typically exhibits multiple exponentials on varying ultrafast time scales. The size of the semiconductor nanoparticle appears to influence the diffusion of the CB electrons and thus their lifetimes. In all studies reported, the observed multiexponential decays have been analyzed and interpreted using purely phenomenological models, in which the individual decays were intuitively assigned to one specific relaxation or loss process. In reality, however, each exponential decay can be a convolution of multiple physical processes. In this Account, we report a universally applicable physical model, constructed by including all known electron dynamic processes, to quantitatively account for the multiexponential decays. We characterize the model as universal, as it can be used to analyze our own TA measurements, as well as data acquired in other laboratories. In our study of TiO2 nanorods photosensitized by Ag platelets, we demonstrate that each of the observed triple-exponential decays corresponds to a convolution of several physical decay processes occurring on similar time scales. The rate of each of the processes can be deconvoluted and determined to construct a complete, physically based model to assess the most important question: How many CB electrons are near the semiconductor surface region and what is their lifetime?The size of the semiconductor is an important consideration. Intuitively, as the semiconductor volume increases, there is more room for CB electrons to diffuse around, which increases their lifetime as annihilation occurs primarily at the surface. Indeed, Tachiya and co-workers previously reported that this lifetime increases with particle size. Nevertheless, while CB electrons live longer in the bulk of the particle, they are only useful when they are at the surface. Overall, what really matters is the CB electrons near the surface region, where the photosensitized functions actually occur. In applying our model to analyze the previously reported size-dependent Au/TiO2 results, we successfully reproduced the observation that larger semiconductor nanoparticles lengthen the lifetime of CB electrons because of diffusion into the bulk. More importantly, however, our model reveals that the size of the semiconductor has almost no influence on the retention of CB electrons near the semiconductor surface. This information is only revealed when all physical processes are quantitatively taken into account for the observed electron dynamics, which is not feasible with a phenomenological approach.

Collisional Relaxation of Highly Vibrationally Excited Acetylene Mediated by the Vinylidene Isomer.

Collisional relaxation of highly vibrationally excited acetylene, generated from the 193 nm photolysis of vinyl bromide with roughly 23,000 cm-1 of nascent vibrational energy, is studied via submicrosecond time-resolved Fourier transform infrared (FTIR) emission spectroscopy. IR emission from vibrationally hot acetylene during collisional relaxation by helium, neon, argon, and krypton rare-gas colliders is recorded and analyzed to deduce the acetylene energy content as a function of time. The average energy lost per collision, ⟨ΔE⟩, is computed using the Lennard-Jones collision frequency. Two distinct vibrational-to-translational (V-T) energy transfer regimes in terms of the acetylene energy are identified. At vibrational energies below 10,000-14,000 cm-1, energy transfer efficiency increases linearly with molecular energy content and is in line with typical V-T behavior in quantity. In contrast, above 10,000-14,000 cm-1, the V-T energy transfer efficiency displays a dramatic and rapid increase. This increase is nearly coincident with the acetylene-vinylidene isomerization limit, which occurs nearly 15,000 cm-1 above the acetylene zero-point energy. Combined quasi-classical trajectory calculations and Schwartz-Slawsky-Herzfeld-Tanczos theory point to a vinylidene contribution being responsible for the large enhancement. This observation illustrates the influence of energetically accessible structural isomers to greatly enhance the energy transfer rates of highly vibrationally excited molecules.

The low-lying electronic states and ultrafast relaxation dynamics of the monomers and J-aggregates of meso-tetrakis (4-sulfonatophenyl)-porphyrins.

The electronic and vibrational spectra of the meso-tetrakis(4-sulfonatophenyl)-porphyrins (TSPP) have been studied computationally using the PFD-3B functional with time-dependent density functional theory for the excited states. The calculated UV-vis absorption and emission spectra in aqueous solution are in excellent agreement with the experimental measurements of both H2TSPP-4 (monomer) at high pH and H4TSPP-2 (forming J-aggregate) at low pH. Moreover, our calculations reveal an infrared absorption at 1900 cm-1 in the singlet and triplet excited states that is absent in the ground state, which is chosen as a probe for transient IR absorption spectroscopy to investigate the vibrational dynamics of the excited state. Specifically, the S2 to S1 excited state internal conversion process time, the S1 state vibrational relaxation time, and the lifetime of the S1 excited electronic state are all quantitatively deduced.

Ag nanoplatelets as efficient photosensitizers for TiO2 nanorods.

The lifetime for injecting hot electrons generated in Ag nanoplatelets to nearby TiO2 nanorods was measured with ultrafast transient IR absorption to be 13.1 ± 1.5 fs, which is comparable to values previously reported for much smaller spherical Ag nanoparticles. Although it was shown that the injection rate decreases as the particle size increases, this observation can be explained by the facts that (1) the platelet has a much larger surface to bulk ratio and (2) the platelet affords a much larger surface area for direct contact with the semiconductor. These two factors facilitate strong Ag-TiO2 coupling (as indicated by the observed broadened surface plasmon resonance band of Ag) and can explain why Ag nanoplatelets have been found to be more efficient than much smaller Ag nanoparticles as photosensitizers for photocatalytic functions. The fast injection rate, together with a stronger optical absorption in comparison with Au and dye molecules, make Ag nanoplatelets a preferred photosensitizer for wide bandgap semiconductors.

Influence of Phase Transitions on Diffusive Molecular Transport Across Biological Membranes.

Phase transitions of lipid bilayer membranes should affect passive transport of molecules. While this hypothesis has been used to design drug-releasing thermosensitive liposomes, the effect has yet to be quantified. Herein, we use time-resolved second harmonic light scattering to measure transport of a molecular cation across membranes of unilamellar liposomes composed of the total lipid extract of E. coli from 9 °C to 36 °C, in which two distinct phase transitions (gel to liquid-disordered phase) have been identified. While the transport rate slowly increases with temperature as a diffusion process, dramatic jumps are observed at 14.7 °C and 27.6 °C, the known phase transitions. The transport rate constant measured as (7.3±0.8)×10-3  s-1 in the liquid-disordered phase at 36 °C is 35-times faster than (2.1±0.2)×10-4  s-1 of the gel phase at 9 °C. For the mixed-phase between these two phases, the measured rates are consistent with a structure of gel domains among a liquid-disordered bulk.

Determination of bacterial surface charge density via saturation of adsorbed ions.

Bacterial surface charge is a critical characteristic of the cell's interfacial physiology that influences how the cell interacts with the local environment. A direct, sensitive, and accurate experimental technique capable of quantifying bacterial surface charge is needed to better understand molecular adaptations in interfacial physiology in response to environmental changes. We introduce here the method of second-harmonic light scattering (SHS), which is capable of detecting the number of molecular ions adsorbed as counter charges on the exterior bacterial surface, thereby providing a measure of the surface charge. In this first demonstration, we detect the small molecular cation, malachite green, electrostatically adsorbed on the surface of representative strains of Gram-positive and Gram-negative bacteria. Surprisingly, the SHS-deduced molecular transport rates through the different cellular ultrastructures are revealed to be nearly identical. However, the adsorption saturation densities on the exterior surfaces of the two bacteria were shown to be characteristically distinct. The negative charge density of the lipopolysaccharide coated outer surface of Gram-negative Escherichia coli (6.6 ± 1.3 nm-2) was deduced to be seven times larger than that of the protein surface layer of Gram-positive Lactobacillus rhamnosus (1.0 ± 0.2 nm-2). The feasibility of SHS-deduced bacterial surface charge density for Gram-type differentiation is presented.

Control of Chemical Reactions through Coherent Excitation of Eigenlevels: A Demonstration via Vibronic Coupling in SO2.

Through coherent excitation of a pair of vibronically coupled eigenlevels, an oscillation of 130 kcal/mol in energy excitation between electronic and vibrational motions (on a time scale of 10-8 s) is created for the triatomic molecule, sulfur dioxide (SO2). The reactivity of the molecule can be influenced depending upon whether the molecule is vibrationally or electronically excited with this substantial amount of energy. The effect of excitation on reactivity is demonstrated through SO2 photodissociation as a function of time following coherent excitation, monitored by multiphoton ionization of the SO product.

Spatially Resolved Membrane Transport in a Single Cell Imaged by Second Harmonic Light Scattering.

We demonstrate that time-resolved second harmonic (SH) light scattering, when applied as an imaging modality, can be used to spatially resolve the adsorption and transport rates of molecules diffusing across the membrane in a living cell. As a representative example, we measure the passive transport of the amphiphilic ion, malachite green, across the plasma membrane in living human dermal fibroblast cells. Analysis of the time-resolved SH images reveals that membrane regions, which appear to be enduring higher stress, exhibit slower transport rates. It is proposed that this stress-transport relation may be a result of local enrichment of membrane rigidifiers as part of a response to maintain membrane integrity under strain.

Collisional Energy Transfer from Vibrationally Excited Hydrogen Isocyanide.

Collisional deactivation of vibrationally excited hydrogen isocyanide (HNC) by inert gas atoms was characterized using nanosecond time-resolved Fourier transform infrared emission spectroscopy. HNC, with an average nascent internal energy of 25.9 ± 1.4 kcal mol-1, was generated following the 193 nm photolysis of vinyl cyanide (CH2CHCN) and collisionally deactivated with the series of inert atomic gases: He, Ar, Kr, and Xe. Time-dependent IR emission allows simultaneous experimental observation of the ν1 NH and ν3 NC stretch emissions from vibrationally excited HNC. Subsequent spectral fit analysis enables direct determination of the average energy of HNC in each spectrum and therefore a measure of the average energy lost per collision, ⟨ΔE⟩, as a function of internal energy. Collisional deactivation of excited HNC is shown to be relatively efficient, exhibiting ⟨ΔE⟩ values more than an order of magnitude larger than comparably sized molecules at similar internal energies. Furthermore, the lighter inert gases are shown to be more efficient quenchers. Both observations can be qualitatively explained by the momentum gap law modeled through the repulsive force dominated vibration-to-translation energy transfer mechanism. The feasibility of efficient collisional deactivation as a contributing factor to the observed overabundance of astrophysical HNC is discussed.

Influence of molecular structure on passive membrane transport: A case study by second harmonic light scattering.

We present an experimental study, using the surface sensitive technique, second harmonic light scattering (SHS), to examine the influence of structure on the propensity of a molecule to passively diffuse across a phospholipid membrane. Specifically, we monitor the relative tendency of the structurally similar amphiphilic cationic dyes, malachite green (MG) and crystal violet (CV), to transport across membranes in living cells (E. coli) and biomimetic liposomes. Despite having nearly identical molecular structures, molecular weights, cationic charges, and functional groups, MG is of lower overall symmetry and consequently has a symmetry allowed permanent dipole moment, which CV does not. The two molecules showed drastically different interactions with phospholipid membranes. MG is observed to readily cross the hydrophobic interior of the bacterial cytoplasmic membrane. Conversely, CV does not. Furthermore, experiments conducted with biomimetic liposomes, constructed from the total lipid extract of E. coli and containing no proteins, show that while MG is able to diffuse across the liposome membrane, CV does not. These observations indicate that the SHS results measured with bacteria do not result from the functions of efflux pumps, but suggests that MG possesses an innate molecular property (which is absent in CV) that allows it to passively diffuse across the hydrophobic interior of a phospholipid membrane.

UV Photolysis of Pyrazine and the Production of Hydrogen Isocyanide.

Photolysis of the diazine heterocycle, pyrazine, following irradiation at 308, 248, and 193 nm was examined using nanosecond time-resolved Fourier transform infrared emission spectroscopy. The resulting time-resolved IR emission spectra reveal that for 308 and 248 nm vibrationally highly excited pyrazine is produced, but no photolysis products were detected. However, at 193 nm excitation, the measured IR emission spectra consist solely of resonances originating from rovibrationally excited photofragments, including acetylene (HCCH), hydrogen cyanide (HCN), and hydrogen isocyanide (HNC), indicating that photofragmentation proceeds from vibrationally highly excited pyrazine on the ground electronic state. Spectral fit analysis of the time-resolved HCN and HNC IR emission band shapes and intensities allowed an estimate of the nascent product population distributions, from which a lower bound estimate of the HNC/HCN branching ratio was deduced as Φ ≥ 0.07. Additionally, ab initio calculations were performed in order to examine the propensity of photoinduced reactions on the ground- and lowest-energy excited-state surfaces. The calculations provide a basis for understanding the wavelength dependence of the UV photolysis of pyrazine, the photolytic production of HNC, and also explain previous experimental observations in the literature.

Effects of Molecular Structure and Solvent Polarity on Adsorption of Carboxylic Anchoring Dyes onto TiO2 Particles in Aprotic Solvents.

Interactions of molecules with the surface of TiO2 particles are of fundamental and technological importance. One example is that the adsorption density and energy of the dye molecules on TiO2 particles affect the efficiency of dye-sensitized solar cells (DSSC). In this work, we present measurements characterizing the adsorption of the two isomers, para-ethyl red (p-ER) and ortho-ethyl red (o-ER), of a dye molecule potentially applicable for DSSC onto TiO2 particles by second harmonic scattering (SHS). It is found that while at the wavelengths used here o-ER has a much bigger molecular hyperpolarizability, p-ER exhibits strong SHS responses but o-ER gives no detectable SHS when the dyes are added to the TiO2 colloids, respectively. This observation indicates that o-ER does not adsorb onto TiO2, likely due to steric hindrance. Furthermore, we investigate how solvents affect the surface adsorption strength and density of p-ER onto TiO2 in four aprotic solvents with varying polarity. The absolute magnitude of the adsorption free energy was found to increase with the specific solvation energy that represents the ability of accepting electrons and solvent polarity. It is likely that resolvation of the solvent molecules displaced by the adsorption of the dye molecule at the surface in stronger electron-accepting and more polar solvents results in a larger adsorption free energy for the dye adsorption.

Modeling Photosensitized Secondary Organic Aerosol Formation in Laboratory and Ambient Aerosols.

Photosensitized reactions involving imidazole-2-carboxaldehyde (IC) have been experimentally observed to contribute to secondary organic aerosol (SOA) growth. However, the extent of photosensitized reactions in ambient aerosols remains poorly understood and unaccounted for in atmospheric models. Here we use GAMMA 4.0, a photochemical box model that couples gas-phase and aqueous-phase aerosol chemistry, along with recent laboratory measurements of the kinetics of IC photochemistry, to analyze IC-photosensitized SOA formation in laboratory and ambient settings. Analysis of the laboratory results of Aregahegn et al. (2013) suggests that photosensitized production of SOA from limonene, isoprene, α-pinene, ß-pinene, and toluene by 3IC* occurs at or near the surface of the aerosol particle. Reactive uptake coefficients were derived from the experimental data using GAMMA 4.0. Simulations of aqueous aerosol SOA formation at remote ambient conditions including IC photosensitizer chemistry indicate less than 0.3% contribution to SOA growth from direct reactions of 3IC* with limonene, isoprene, α-pinene, ß-pinene, and toluene, and an enhancement of less than 0.04% of SOA formation from other precursors due to the formation of radicals in the bulk aerosol aqueous phase. Other, more abundant photosensitizer species, such as humic-like substances (HULIS), may contribute more significantly to aqueous aerosol SOA production.

Photoactivated Production of Secondary Organic Species from Isoprene in Aqueous Systems.

Photoactivated reactions of organic species in atmospheric aerosol particles are a potentially significant source of secondary organic aerosol material (SOA). Despite recent progress, the dominant chemical mechanisms and rates of these reactions remain largely unknown. In this work, we characterize the photophysical properties and photochemical reaction mechanisms of imidazole-2-carboxaldehyde (IC) in aqueous solution, alone and in the presence of isoprene. IC has been shown previously in laboratory studies to participate in photoactivated chemistry in aerosols, and it is a known in-particle reaction product of glyoxal. Our experiments confirmed that the triplet excited state of IC is an efficient triplet photosensitizer, leading to photosensitization of isoprene in aqueous solution and promoting its photochemical processing in aqueous solution. Phosphorescence and transient absorption studies showed that the energy level of the triplet excited state of IC (3IC*) was approximately 289 kJ/mol, and the lifetime of 3IC* in water under ambient temperature is 7.9 µs, consistent with IC acting as an efficient triplet photosensitizer. Laser flash photolysis experiments displayed fast quenching of 3IC* by isoprene, with a rate constant of (2.7 ± 0.3) × 109 M-1 s-1, which is close to the diffusion-limited rate in water. Mass spectrometry analysis showed that the products formed include IC-isoprene adducts, and chemical mechanisms are discussed. Additionally, oxygen quenches 3IC* with a rate constant of (3.1 ± 0.1) × 109 M-1 s-1.

Chemically Induced Changes to Membrane Permeability in Living Cells Probed with Nonlinear Light Scattering.

Second-harmonic light scattering (SHS) permits characterization of membrane-specific molecular transport in living cells. Herein, we demonstrate the use of time-resolved SHS for quantifying chemically induced enhancements in membrane permeability. As proof of concept, we examine the enhanced permeability of the cytoplasmic membrane in living Escherichia coli following addition of extracellular adenosine triphosphate (ATPe). The transport rate of the hydrophobic cation, malachite green, increases nearly an order of magnitude following addition of 0.1 mM ATPe. The absence of an ATPe-enhanced permeability in liposomes strongly suggests the induced effect is protein-mediated. The utility of SHS for elucidating the mechanism of action of antimicrobials is discussed.

Stabilized phase detection of heterodyne sum frequency generation for interfacial studies.

We present a collinear-geometry heterodyne sum frequency generation (HD-SFG) method for interfacial studies. The HD detection is based on a collinear SFG configuration, in which picosecond visible and femtosecond IR beams are used to first produce a strong local oscillator and then to generate weak SFG signals from an interface. A time-delay compensator, consisting of an MgF2 window, is placed before the sample to introduce the time delay between the local oscillator and the interfacial SFG signals for spectral interferometry. Our HD-SFG method exhibits advantages of long-time phase stability. It is not sensitive to sample heights, does not require reflection correction, and is easy to implement.

Spectral reconstruction analysis for enhancing signal-to-noise in time-resolved spectroscopies.

We demonstrate a new spectral analysis for the enhancement of the signal-to-noise ratio (SNR) in time-resolved spectroscopies. Unlike the simple linear average which produces a single representative spectrum with enhanced SNR, this Spectral Reconstruction analysis (SRa) improves the SNR (by a factor of ca. 0.6√n) for all n experimentally recorded time-resolved spectra. SRa operates by eliminating noise in the temporal domain, thereby attenuating noise in the spectral domain, as follows: Temporal profiles at each measured frequency are fit to a generic mathematical function that best represents the temporal evolution; spectra at each time are then reconstructed with data points from the fitted profiles. The SRa method is validated with simulated control spectral data sets. Finally, we apply SRa to two distinct experimentally measured sets of time-resolved IR emission spectra: (1) UV photolysis of carbonyl cyanide and (2) UV photolysis of vinyl cyanide.

Chemical activation through super energy transfer collisions.

Can a molecule be efficiently activated with a large amount of energy in a single collision with a fast atom? If so, this type of collision will greatly affect molecular reactivity and equilibrium in systems where abundant hot atoms exist. Conventional expectation of molecular energy transfer (ET) is that the probability decreases exponentially with the amount of energy transferred, hence the probability of what we label "super energy transfer" is negligible. We show, however, that in collisions between an atom and a molecule for which chemical reactions may occur, such as those between a translationally hot H atom and an ambient acetylene (HCCH) or sulfur dioxide, ET of chemically significant amounts of energy commences with surprisingly high efficiency through chemical complex formation. Time-resolved infrared emission observations are supported by quasi-classical trajectory calculations on a global ab initio potential energy surface. Results show that ∼10% of collisions between H atoms moving with ∼60 kcal/mol energy and HCCH result in transfer of up to 70% of this energy to activate internal degrees of freedom.

Second harmonic light scattering from the surface of colloidal objects: theory and applications.

Because properties of colloids containing micro- and nano-particles are much influenced by the structure of, and interactions occurring at, the particle surface, it is important to be able to characterize the particle surface in situ and nondestructively. Nonlinear light scattering from colloidal particles has been developed into a powerful and versatile technique for characterizing particle surfaces since the first demonstration of the detection of second harmonic generation from molecules adsorbed on micrometer-sized colloidal particles by Eisenthal and co-workers (Wang, H.; Yan, E. C. Y.; Borguet, E.; Eisenthal, K. B. Second Harmonic Generation from the Surface of Centrosymmetric Particles in Bulk Solution. Chem. Phys. Lett. 1996, 259, 15-20). At present, second harmonic light scattering from the particle surface can be quantitatively described by theoretical models and used to measure the adsorption kinetics, molecular structure, and reaction rates at the surfaces of a variety of micrometer- to nanometer-sized particles, including biological cells.