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41.
Time-of-flight (TOF) spectra of photofragment H atoms from the photodissociation of water ice films at 193 nm were measured for amorphous and polycrystalline water ice films with and without dosing of hydrogen chloride at 100-145 K. The TOF spectrum is sensitive to the surface morphology of the water ice film because the origin of the H atom is the photodissociation of dimerlike water molecules attached to the ice film surfaces. Adsorption of HCl on a polycrystalline ice film was found to induce formation of disorder regions on the ice film surface at 100-140 K, while the microstructure of the ice surface stayed of polycrystalline at 145 K with adsorption of HCl. The TOF spectra of photofragment Cl atoms from the 157 nm photodissociation of neutral HCl adsorbed on water ice films at 100-140 K were measured. These results suggest partial dissolution of HCl on the ice film surface at 100-140 K. 相似文献
42.
Mitsuharu Higashiguchi Kenya Shimada Yuichi Miura Xiaoyu Cui Hirofumi Namatame 《Surface science》2007,601(18):4005-4009
High-resolution angle-resolved photoemission spectroscopy (ARPES) has been conducted to study the Shockley state (SS) in ferromagnetic Ni(1 1 1) located at the point of the surface Brillouin zone. We have determined the Fermi wave vector and Fermi energy of the state with excitation photon energies of hν = 6.9-27.5 eV. On the basis of ARPES spectral shape analyses, we have found significant electron-electron interaction in the SS. 相似文献
43.
Kinugawa T Enami S Yabushita A Kawasaki M Hoffmann MR Colussi AJ 《Physical chemistry chemical physics : PCCP》2011,13(11):5144-5149
The hydrolytic disproportionation of gaseous NO(2) on water's surface (2 NO(2) + H(2)O → HONO + NO(3)(-) + H(+)) (R1) has long been deemed to play a key, albeit unquantifiable role in tropospheric chemistry. We recently found that (R1) is dramatically accelerated by anions in experiments performed on aqueous microjets monitored by online electrospray mass spectrometry. This finding let us rationalize unresolved discrepancies among previous laboratory results and suggested that under realistic environmental conditions (R1) should be affected by everpresent surfactants. Herein, we report that NO(2)(g) uptake is significantly enhanced by cationic surfactants, weakly inhibited by fulvic acid (FA, a natural polycarboxylic acid) and anionic surfactants, and unaffected by 1-octanol. Surfactants appear to modulate interfacial anion coverage via electrostatic interactions with charged headgroups. We show that (R1) should be the dominant mechanism for the heterogeneous conversion of NO(2)(g) to HONO under typical atmospheric conditions throughout the day. The photoinduced reduction of NO(2) into HONO on airborne soot might play a limited role during daytime. 相似文献
44.
Hayase S Yabushita A Kawasaki M Enami S Hoffmann MR Colussi AJ 《The journal of physical chemistry. A》2011,115(19):4935-4940
We report that rates of I(2)(g) emissions, measured via cavity ring-down spectroscopy, during the heterogeneous ozonation of interfacial iodide: I(-)(surface, s) + O(3)(g) + H(+)(s) →→ I(2)(g), are enhanced several-fold, whereas those of IO·(g) are unaffected, by the presence of undissociated alkanoic acids on water. The amphiphilic weak carboxylic acids appear to promote I(2)(g) emissions by supplying the requisite interfacial protons H(+)(s) more efficiently than water itself, at pH values representative of submicrometer marine aerosol particles. We infer that the organic acids coating aerosol particles ejected from ocean's topmost films should enhance I(2)(g) production in marine boundary layers. 相似文献
45.
D. Yamano Y. Sakamoto A. Yabushita M. Kawasaki I. Morino G. Inoue 《Applied physics. B, Lasers and optics》2009,97(2):523-528
Buffer-gas pressure broadening for the P(1), Q(1), R(0) and R(1) transitions in the 2ν
3 band of CH4 was investigated in the 1660 nm region. The pressure broadening coefficients, γ(gas), were determined for a variety of buffer gases: N2, O2, He, Ne, Ar, Kr and Xe. The γ values generally increased with increasing polarizability of the buffer gases. γ(air) are 0.056(2) for P(1), 0.056(1) for R(0), 0.061(1) for R(1) and 0.059(1) for Q(1) in units of cm−1 atm−1 where numbers in parentheses are one standard deviation in units of the last digits quoted. The temperature dependent parameter
(broadening exponent) for air is 0.84(7) for P(1) within the temperature range 233–298 K. 相似文献
46.
Summary: Controlled copolymerization of polar (meth)acrylates with non-polar olefin monomers (1-octene, norbornene, vinylcyclohexane) was studied by ARGET (activators regenerated by electron transfer) ATRP (atom transfer radical polymerization). When a normal ATRP of n-butyl acrylate (nBA) and 1-octene was conducted, the polymerization resulted in relatively low conversion, limited control over the polymerization process and high polydispersity (PDI > 1.6). This was due to formation of a dormant species, by reaction of 1-octene radicals with Cu(II) deactivator, that could not be reactivated. However, in ARGET ATRP with 10 ppm amounts of Cu-based catalyst, higher yields and a better controlled copolymerization was obtained (PDI < 1.4), because the low concentration of Cu(II) deactivator reduced the formation of the non-reactive dormant species. The influence of the amount of Cu catalyst, ligand structure, initiators with different halogens, the reaction temperature, and monomer feed ratio were also investigated for ARGET ATRP. In copolymerization of (meth)acrylates with non-polar alkenes, the level of control and the total conversion in ARGET ATRP were higher than those for normal ATRP. 相似文献
47.
48.
In an error detection optical system for optical pick-ups using a parallel plane type half mirror, influence on the differential phase detection (DPD) signal by a coma aberration was simulated. The coma aberration deforms the spot profile on the photodetector and influences the DPD signal level characteristics and the offset characteristics with respect to the objective lens shift. In the 4-segment-type DPD, the coma aberration caused by a half mirror 2.75 mm thick hardly affects the DPD signal if the photodetector is not misaligned. On the other hand, the 2-segment-type DPD has a small offset variation with respect to the objective lens shift and a large variation of the DPD signal level against the misalignment of the photodetector in comparison with the 4-segment-type DPD when there is no coma aberration. In the presence of a coma aberration, however, these variations of the 2-segment-type DPD are suppressed by choosing a pair of elements without the coma apex part of the spot. 相似文献
49.
To gain insight on the absorption intensities, as well as the direction of the transition moment for the OH stretching vibration in alcohols and acids, we performed detailed analyses for nitric acid, acetic acid, methanol, tert-butyl alcohol, water, and OH radical. We obtained both the potential energy surface and the dipole moment function (DMF) by the B3LYP method and performed quantum mechanical vibrational calculation using the grid variational method based on the local mode model. In this work, we employed the sum rule of the absorption intensities for the one-dimensional (1-D) vibrational Hamiltonian to construct an effective 1-D DMF, which is responsible for the total sum of the overtone intensities. The direction of this effective DMF was found to be tilted away from the OH bond by about 30 degrees for the polyatomic molecules. The nonlinearity of the DMFs in the directions parallel and perpendicular to the OH bond is discussed to rationalize the tilting. Furthermore, we analyzed the effective 1-D DMFs with the vibrational wave function expansion method and derived the effective portion of the 1-D DMF that is responsible for the overtone transition moment. 相似文献
50.
Geometry optimizations of perepoxide, 1,4-diradical, zwitterion and dioxetane for the 1,1-diaminoethylene plus singlet molecular oxygen system were performed using the energy gradients of the HF 4-31G and STO-3G solutions. The zwitterion (ZW) is more stable than the perepoxide and σπ-diradical (DR) intermediates (at the 4-31G level), supporting the previous ZW mechanism for photoovygenation reactions of N-activated C-C double bonds 相似文献