On Second-Order Vibrational Lineshapes of the Air/Water Interface

We explore by means of modeling how absorptive-dispersive mixing between the second- and third-order terms modify the imaginary chi(2)total responses from air/water interfaces under conditions of varying charge densities and ionic strength. To do so, we use published Im(chi(2)) and chi(3) spectra of the neat air/water interface that were obtained either from computations or experiments. We find that the chi(2)total spectral lineshapes corresponding to experimentally measured spectra contain significant contributions from both interfacial chi(2) and bulk chi(3) terms at interfacial charge densities equivalent to less than 0.005% of a monolayer of water molecules, especially in the 3100 wavenumber to 3300 wavenumber frequency region. Additionally, the role of short-range static dipole potentials is examined under conditions mimicking brine. Our results indicate that surface potentials, if indeed present at the air/water interface, manifest themselves spectroscopically in the tightly bonded H-bond network observable in the 3200 wavenumber frequency range.Comment: Pre-edited version, 21 pages, 3 figures, supporting information available upon reques

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 .Comment: Pre-edited version, 15 manuscript pages, 2 tables, 5 figures. Supporting Information available up request to the corresponding autho

Differentiation of Verticillium dahliae populations on the basis of vegetative compatibility and pathogenicity on cotton

Abstract Complementary auxotrophic nitrate-nonutilizing (nit) mutants were used to investigate vegetative compatibility within 27 strains of Verticillium dahliae isolated from several hosts originating from Africa, Asia, Europe and the United States. Using about 500 nit mutants generated from these strains, three vegetative compatibility groups, 1 , 2 and 4, were identified. Simultaneously, virulence of each strain was assessed on cultivars of Gossypium hirsutum, G. barbadense and G. arboreum, based upon Foliar Alteration Index (FAI) and Browning Index (BI) estimation. The strains in VCGl were of both the cottondefoliating pathotype and race 3 (on cotton) but were non pathogenic on tomato; those in VCG2 and VCG4 were of the nondefoliating pathotype and belonged to different races on cotton and on tomato. Hyaline mutants deriving from parental wild-type strain showed differences in pathogenicity but were always assigned to the parental VCG. A relationship was established between VCGs and the taxonomic position of host plants. Data from nit pairings indicated that the sub-populations of V. dahliae (VCGS) may not be completely isolated genetically. .