arXiv subjects

Paul E. Ohno

Publications and source records attributed to Paul E. Ohno.

10 recordsLinked to original sources

arXiv2026

Tropospheric Ozone Formation Potential and Related Design Considerations for Radiative Coolers

Recently, radiative coolers have been widely explored for reducing cooling loads or lowering temperatures in buildings, and at urban scales as a heat-mitigation measure. However, the potential impacts of radiative cooler deployment on the chemical composition of the atmosphere remain largely unexplored. A defining feature of recently-designed radiative coolers is their high ultraviolet (UV) reflectance, which is required for sub-ambient cooling under strong sunlight. Yet, wide adoption of such UV-reflective radiative coolers could substantially increase the UV actinic flux in the atmosphere above. This, in turn, may affect tropospheric ozone concentrations, particularly in urban atmospheres with high NOx concentrations. Here, as a case study, we use a 0-dimensional photochemical box model, constrained by field measurements of meteorological conditions and chemical concentrations in the urban environment of Houston, Texas, to explore the potential impact of the widespread use of UV-reflective radiative coolers on ozone concentrations. Our calculations show that complete deployment of radiative coolers may increase tropospheric ozone levels by as much as 30% during specific meteorological conditions in Houston. Informed by the wavelength-dependent modelling results, we propose specific designs, namely pigmented radiative coolers with different UV reflectances, and UV-absorptive visible-reemitting fluorescent radiative coolers, that could minimize negative ozone formation while retaining appreciable cooling performance. Our results motivate further study on the effects of widespread deployment of radiative cooling designs like superwhite roof paints on air quality, and materials that simultaneously minimize adverse photochemical impact and maximize cooling performance.

physics.ao-ph↗

arXiv2021

Stern and Diffuse Layer Interactions During Ionic Strength Cycling

Second harmonic generation amplitude and phase measurements are acquired in real time from fused silica:water interfaces that are subjected to ionic strength transitions conducted at pH 5.8. In conjunction with atomistic modeling, we identify correlations between structure in the Stern layer, encoded in the total second-order nonlinear susceptibility, chi(2)tot, and in the diffuse layer, encoded in the product of chi(2)tot and the total interfacial potential, phi(0)tot. chi(2)tot:phi(0)tot correlation plots indicate that the dynamics in the Stern and diffuse layers are decoupled from one another under some conditions (large change in ionic strength), while they change in lockstep under others (smaller change in ionic strength) as the ionic strength in the aqueous bulk solution varies. The quantitative structural and electrostatic information obtained also informs on the molecular origin of hysteresis in ionic strength cycling over fused silica. Atomistic simulations suggest a prominent role of contact ion pairs (as opposed to solvent-separated ion pairs) in the Stern layer. Those simulations also indicate that net water alignment is limited to the first 2 nm from the interface, even at 0 M ionic strength, highlighting water's polarization as an important contributor to nonlinear optical signal generation.

cond-mat.mtrl-sci↗

arXiv2021

A New Imaginary Term in the 2nd Order Nonlinear Susceptibility from Charged Interfaces

Non-resonant second harmonic generation phase and amplitude measurements obtained from the silica:water interface at varying pH and 0.5 M ionic strength point to the existence of a nonlinear susceptibility term, which we call chi(3)X, that is associated with a 90 deg phase shift. Including this contribution in a model for the total effective second-order nonlinear susceptibility produces reasonable point estimates for interfacial potentials and second-order nonlinear susceptibilities when chi(3)Xis about 1.5 times chi(3)water. A model without this term and containing only traditional chi(2) and chi(3) terms cannot recapitulate the experimental data. The new model also provides a demonstrated utility for distinguishing apparent differences in the second-order nonlinear susceptibility when the electrolyte is NaCl vs MgSO4, pointing to the possibility of using HD-SHG to investigate ion-specificity in interfacial processes.

physics.chem-ph↗

arXiv2019

Energy Conversion via Metal Nanolayers

Current approaches for electric power generation from nanoscale conducting or semi-conducting layers in contact with moving aqueous droplets are promising as they show efficiencies of around 30 percent, yet, even the most successful ones pose challenges regarding fabrication and scaling. Here, we report stable, all-inorganic single-element structures synthesized in a single step that generate electrical current when alternating salinity gradients flow along its surface in a liquid flow cell. 10 nm to 30 nm thin nanolayers of iron, vanadium, or nickel produce several tens of mV and several microA cm^-2 at aqueous flow velocities of just a few cm s^-1. The principle of operation is strongly sensitive to charge-carrier motion in the thermal oxide nano-overlayer that forms spontaneously in air and then self terminates. Indeed, experiments suggest a role for intra-oxide electron transfer for Fe, V, and Ni nanolayers, as their thermal oxides contain several metal oxidation states, whereas controls using Al or Cr nanolayers, which self-terminate with oxides that are redox inactive under the experimental conditions, exhibit dramatically diminished performance. The nanolayers are shown to generate electrical current in various modes of application with moving liquids, including sliding liquid droplets, salinity gradients in a flowing liquid, and in the oscillatory motion of a liquid without a salinity gradient.

physics.app-ph↗

arXiv2019

Specifics about Specific Ion Adsorption from Heterodyne-Detected Second Harmonic Generation

Ion specific outcomes at aqueous interfaces remain among the most enigmatic phenomena in interfacial chemistry. Here, charged fused silica/water interfaces have been probed by homodyne- and heterodyne-detected (HD) second harmonic generation (SHG) spectroscopy at pH 7 and pH 5.8 and for concentrations of LiCl, NaCl, NaBr, NaI, KCl, RbCl, and CsCl ranging from 10 mc microM to several 100 mM. For ionic strengths around 0.1 mM to 1 mM, SHG intensities increase reversibly by up to 15% compared to the condition of zero added salt because of optical phase matching and electrical double layer. For ionic strengths above 1 mM, use of any combination of cations and anions produces decreases in SHG response by as much as 50%, trending with ion softness when compared to the condition of zero added salt. Gouy- Chapman model fits to homodyned SHG intensities for the alkali halides studied here show charge densities increase significantly with decreasing cation size. HD-SHG measurements indicate diffuse layer properties probed by the SHG process are invariant with ion identity, while Stern layer properties, as reported by chi(2), are subject to ion specificity for the ions surveyed in this work in the order of chi(2)RbCl = 1/2 chi(2)NaCl = 1/4 chi(2)NaI .

physics.chem-ph↗

arXiv2019

Beyond the Gouy-Chapman Model with Heterodyne-Detected Second Harmonic Generation

We report ionic strength-dependent phase shifts in second harmonic generation (SHG) signals from charged interfaces that verify a recent model in which dispersion between the fundamental and second harmonic beams modulates observed signal intensities. We show how phase information can be used to unambiguously separate the chi(2) and interfacial potential-dependent chi(3) terms that contribute to the total signal and provide a path to test primitive ion models and mean field theories for the electrical double layer with experiments to which theory must conform. Finally, we demonstrate the new method on supported lipid bilayers and comment on the ability of our new instrument to identify hyper-Rayleigh scattering contributions to common homodyne SHG measurements in reflection geometries.

physics.app-ph↗

arXiv2018

Hydrogen Bond Networks Near Supported Lipid Bilayers from Vibrational Sum Frequency Generation Experiments and Atomistic Simulations

We report vibrational sum frequency generation spectra from supported lipid bilayers in which the OH and the CH stretching signals are probed at different salt concentrations. Atomistic simulations show a negligible impact of salt on the OH stretching spectra, indicating the observed SFG intensity changes are due to chi(3) and potential dependent contributions. These are further analyzed in the contact of exact-zero reference states. Further experiments and simulations identify specific hydrogen bonding interactions between interfacial water molecules at the PC head group of the zwitterionic DMPC lipids at 3200 wavenumbers.

cond-mat.soft↗

arXiv2017

Relative Permittivity in the Electrical Double Layer from Nonlinear Optics

Second harmonic generation (SHG) spectroscopy has been applied to probe the fused silica/water interface at pH 7 and the uncharged 11bar02 sapphire/water interface at pH 5.2 in contact with aqueous solutions of NaCl, NaBr, NaI, KCl, RbCl, and CsCl as low as several 10 microM. For ionic strengths up to about 0.1 mM, the SHG responses were observed to increase, reversibly for all salts surveyed, when compared to the condition of zero salt added. Further increases in the salt concentration led to monotonic decreases in the SHG response. The SHG increases followed by decreases are found to be consistent with recent reports of phase interference and phase matching in nonlinear optics. By varying the relative permittivity employed in common mean field theories used to describe electrical double layers, and by comparing our results to available literature data, we find that models recapitulating the experimental observations are ones in which 1) the relative permittivity of the diffuse layer is that of bulk water, with other possible values as low as 30, 2) the surface charge density varies with salt concentration, and 3) the charge in the Stern layer or its thickness vary with salt concentration. We also note that the experimental data exhibit sensitivity depending on whether the salt concentration is increased from low to high values or decreased from high to low values, which, however, is not borne out in the fits, at least within the current uncertainties associated with the model point estimates.

cond-mat.mtrl-sci↗

arXiv2017

Second-Order Spectral Lineshapes from Charged Interfaces

Second-order nonlinear spectroscopy has proven to be a powerful tool in elucidating key chemical and structural characteristics at a variety of interfaces. However, the presence of interfacial potentials may lead to complications regarding the interpretation of second harmonic and vibrational sum frequency generation responses from charged interfaces due to mixing of absorptive and dispersive contributions. Here, we examine by means of mathematical modeling how this interaction influences second-order spectral lineshapes. We discuss our findings in the context of reported nonlinear optical spectra obtained from charged water/air and solid/liquid interfaces and demonstrate the importance of accounting for the interfacial potential-dependent \c{hi}(3) term in interpreting lineshapes when seeking molecular information from charged interfaces using second-order spectroscopy.

cond-mat.mtrl-sci↗

arXiv2016

Phase-referenced Nonlinear Spectroscopy of the alpha-Quartz/Water Interface

Probing the polarization of water molecules at charged interfaces by second harmonic generation spectroscopy has been heretofore limited to isotropic materials. Here, we report non-resonant nonlinear optical measurements at the interface of anisotropic z-cut α-quartz and water under conditions of dynamically changing ionic strength and bulk solution pH. We find that the product of the third-order susceptibility and the interfacial potential, \c{hi}(3). Φ(0), is given by ( \c{hi}(3)-i\c{hi}(3)). Φ(0), and that the interference between this product and the second-order susceptibility of bulk quartz depends on the rotation angle of α-quartz around the z-axis. Our experiments show that this newly identified term, i\c{hi}(3). Φ(0), which is out of phase from the surface terms, is of bulk origin. The possibility of internally phase referencing the interfacial response for the interfacial orientation analysis of species or materials in contact with α-quartz is discussed along with the implications for conditions of resonance enhancement.

cond-mat.other↗