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Herein, we report structural, computational, and conductivity studies on urea-directed self-assembled iodinated triphenylamine (TPA) derivatives. Despite numerous reports of conductive TPAs, the challenges of correlating their solid-state assembly with charge transport properties hinder the efficient design of new materials. In this work, we compare the assembled structures of a methylene urea bridged dimer of di-iodo TPA (1) and the corresponding methylene urea di-iodo TPA monomer (2) with a di-iodo mono aldehyde (3) control. These modifications lead to needle shaped crystals for 1 and 2 that are organized by urea hydrogen bonding, π⋯π stacking, I⋯I, and I⋯π interactions as determined by SC-XRD, Hirshfeld surface analysis, and X-ray photoelectron spectroscopy (XPS). The long needle shaped crystals were robust enough to measure the conductivity by two contact probe methods with 2 exhibiting higher conductivity values (∼6 × 10 −7 S cm −1 ) compared to 1 (1.6 × 10 −8 S cm −1 ). Upon UV-irradiation, 1 formed low quantities of persistent radicals with the simple methylurea 2 displaying less radical formation. The electronic properties of 1 were further investigated using valence band XPS, which revealed a significant shift in the valence band upon UV irradiation (0.5–1.9 eV), indicating the potential of thesemore »materials as dopant free p-type hole transporters. The electronic structure calculations suggest that the close packing of TPA promotes their electronic coupling and allows effective charge carrier transport. Our results show that ionic additives significantly improve the conductivity up to ∼2.0 × 10 −6 S cm −1 in thin films, enabling their implementation in functional devices such as perovskite or solid-state dye sensitized solar cells.« less

Abstract Linearized wave solutions on the equatorial beta plane are examined in the presence of a background meridional moisture gradient. Of interest is a slow, eastward-propagating n = 1 mode that is unstable at planetary scales and only exists for a small range of zonal wavenumbers ( ). The mode dispersion curve appears as an eastward extension of the westward-propagating equatorial Rossby wave solution. This mode is therefore termed the eastward-propagating equatorial Rossby wave (ERW). The zonal wavenumber-2 ERW horizontal structure consists of a low-level equatorial convergence center flanked by quadrupole off-equatorial gyres, and resembles the horizontal structure of the observed MJO. An analytic, leading-order dispersion relationship for the ERW shows that meridional moisture advection imparts eastward propagation, and that the smallness of a gross moist stability–like parameter contributes to the slow phase speed. The ERW is unstable near planetary scales when low-level easterlies moisten the column. This moistening could come from either zonal moisture advection or surface fluxes or a combination thereof. When westerlies instead moisten the column, the ERW is damped and the westward-propagating long Rossby wave is unstable. The ERW does not exist when the meridional moisture gradient is too weak. A moist static energy budget analysismore »shows that the ERW scale selection is partly due to finite-time-scale convective adjustment and less effective zonal wind–induced moistening at smaller scales. Similarities in the phase speed, preferred scale, and horizontal structure suggest that the ERW is a beta-plane analog of the MJO.« less

Abstract Purpose of Review: Review our current understanding of how precipitation is related to its thermodynamic environment, i.e., the water vapor and temperature in the surroundings, and implications for changes in extremes in a warmer climate. Recent Findings: Multiple research threads have i) sought empirical relationships that govern onset of strong convective precipitation, or that might identify how precipitation extremes scale with changes in temperature; ii) examined how such extremes change with water vapor in global and regional climate models under warming scenarios; iii) identified fundamental processes that set the characteristic shapes of precipitation distributions. Summary: While water vapor increases tend to be governed by the Clausius-Clapeyron relationship to temperature, precipitation extreme changes are more complex and can increase more rapidly, particularly in the tropics. Progress may be aided by bringing separate research threads together and by casting theory in terms of a full explanation of the precipitation probability distribution.

Abstract Entrainment of dry tropospheric air can dilute cloud buoyancies and strongly affect the occurrence and intensity of convection. To measure this dry air influence on tropical precipitation, rainfall values that would occur when convection is “protected” from dry air dilution are estimated. An empirical relationship between tropical oceanic precipitation and entraining buoyancy in the lower troposphere (from the surface to 600 hPa) is leveraged. Protected buoyancies are computed by allowing a plume model to entrain saturated air at environmental temperature. These buoyancies are then used to estimate precipitation from protected convection. In most regions, the protected precipitation greatly exceeds the observed precipitation. Warm waters adjoining continents display striking disparities between observed and protected rainfall pointing to rainfall climatologies severely limited by dry air. The most prominent of these regions include the Red Sea and the Persian Gulf, followed by the Caribbean Sea, the Gulf of Mexico, and the seas surrounding the Maritime Continent. We test if similar large precipitation values are realizable in the Community Atmospheric Model (CAM5), wherein the parameterized convection in small (~2° × 2°) pockets is allowed to only entrain saturated air. The precipitation within these pockets shows strong enhancement that is maintained over time, andmore »is compensated by slight reductions in neighboring regions. In the model, protecting convection yields larger precipitation values over ocean than over land; protected precipitation also intensifies in a uniform SST warming experiment. The model experiments suggest that protected pockets in numerical simulations could be used to mimic the consequences of meteorological protection—from closed circulation or moisture shielding effects—that generate extreme precipitation.« less

Abstract Convective quasi-equilibrium (QE) and weak temperature gradient (WTG) balances are frequently employed to study the tropical atmosphere. This study uses linearized equatorial beta-plane solutions to examine the relevant regimes for these balances. Wave solutions are characterized by moisture–temperature ratio ( q – T ratio) and dominant thermodynamic balances. An empirically constrained precipitation closure assigns different sensitivities of convection to temperature ( ε t ) and moisture ( ε q ). Longwave equatorial Kelvin and Rossby waves tend toward the QE balance with q – T ratios of ε t : ε q that can be ~1–3. Departures from strict QE, essential to both precipitation and wave dynamics, grow with wavenumber. The propagating QE modes have reduced phase speeds because of the effective gross moist stability m eff , with a further reduction when ε t > 0. Moisture modes obeying the WTG balance and with large q – T ratios (>10) emerge in the shortwave regime; these modes exist with both Kelvin and Rossby wave meridional structures. In the υ = 0 case, long propagating gravity waves are absent and only emerge beyond a cutoff wavenumber. Two bifurcations in the wave solutions are identified and used to locate themore »spatial scales for QE–WTG transition and gravity wave emergence. These scales are governed by the competition between the convection and gravity wave adjustment times and are modulated by m eff . Near-zero values of m eff shift the QE–WTG transition wavenumber toward zero. Continuous transitions replace the bifurcations when m eff < 0 or moisture advection/WISHE mechanisms are included, but the wavenumber-dependent QE and WTG balances remain qualitatively unaltered. Rapidly decaying convective/gravity wave modes adjust to the slowly evolving QE/WTG state in the longwave/shortwave regimes, respectively.« less

Abstract Observations have shown that tropical convection is influenced by fluctuations in temperature and moisture in the lower free troposphere (LFT; 600–850 hPa), as well as moist enthalpy (ME) fluctuations beneath the 850 hPa level, referred to as the deep boundary layer (DBL; 850–1000 hPa). A framework is developed that consolidates these three quantities within the context of the buoyancy of an entraining plume. A “plume buoyancy equation” is derived based on a relaxed version of the weak temperature gradient (WTG) approximation. Analysis of this equation using quantities derived from the Dynamics of the Madden–Julian Oscillation (DYNAMO) sounding array data reveals that processes occurring within the DBL and the LFT contribute nearly equally to the evolution of plume buoyancy, indicating that processes that occur in both layers are critical to the evolution of tropical convection. Adiabatic motions play an important role in the evolution of buoyancy both at the daily and longer time scales and are comparable in magnitude to horizontal moisture advection and vertical moist static energy advection by convection. The plume buoyancy equation may explain convective coupling at short time scales in both temperature and moisture fluctuations and can be used to complement the commonly used moist staticmore »energy budget, which emphasizes the slower evolution of the convective envelope in tropical motion systems.« less