Isomer-selected photoreactions of gas-phase cluster ions

We have developed an apparatus for investigating isomer-selected photodissociation reactions by ion mobility spectrometry coupled with time-of-flight mass spectrometry. By using this apparatus we optimized ion intensities under isomer-separation condition for carbon cluster ions. Among ions having linear and cyclic isomers, we demonstrated dissociation of isomer-selected C₉ ⁺ ion at 355-nm photon irradiation. As a result we observed marked difference in the dissociation pathways between from linear isomer and from cyclic isomer. For the purpose of adopting this technique to metal-ligand cluster ions, we also investigated mobility spectrometry of vanadium metal ions with Ar, in addition to electronic state separation for free atomic ions.     

Coherent state approach to the cross-collisional effects in the population dynamics of a two-mode Bose–Einstein condensate

We reanalyze the non-linear population dynamics of a Bose–Einstein condensate (BEC) in a double well trap considering a semiclassical approach based on a time dependent variational principle applied to coherent states associated to SU(2) group. Employing a two-mode local approximation and hard sphere type interaction, we show in the Schwinger’s pseudo-spin language the occurrence of a fixed point bifurcation that originates a separatrix of motion on a sphere. This separatrix corresponds to the borderline between two dynamical regimes of Josephson oscillations and mesoscopic self-trapping. We also consider the effects of interaction between particles in different wells, known as cross-collisions. Such terms are usually neglected for traps sufficiently far apart, but recently it has been shown that they contribute to the effective tunneling constant with a factor growing linearly with the particle number. This effect changes considerably the effective tunneling of the system for sufficiently large number of trapped atoms, in perfect accord with experimental data. Finally, we identify analytically the transition parameter associated to the bifurcation in the generalized phase space of the model with cross-collision terms, and show how the dynamical regime depends on the initial conditions of the system and the collisional parameters values.     

Photoinduced magnetization in copper octacyanomolybdate

This article describes the studies of a photomagnetic cyanide-bridged Cu-Mo bimetallic assembly, Cu(II)(2)[Mo(IV)(CN)(8)].8H(2)O (Cu(II), S = (1)/(2); Mo(IV), S = 0) (1), which has an intervalence transfer (IT) band from Mo(IV)-CN-Cu(II) to Mo(V)-CN-Cu(I) around 480 nm. Wide-angle X-ray scattering and X-ray spectroscopic studies provide precise information about the 3D connectivity and the local environment of the transition metal ions. Irradiating with blue light causes solid 1 to exhibit a spontaneous magnetization (Curie temperature = 25 K). The thermal reversibility is carefully studied and shows the long-time stability of the photoinduced state up to 100 K. Photoreversibility is also observed; i.e., the magnetization is induced by irradiation with light below 520 nm, while the magnetization is reduced by irradiation with light above 520 nm. The UV-vis absorption spectrum after irradiation shows a decrease of the IT band and the appearance of the reverse-IT band in the region of 600-900 nm (lambda(max) = 710 nm). This UV-vis absorption spectrum is recovered to the original spectrum by irradiation with 658-, 785-, and 840-nm light. In this photomagnetic effect, the excitation of the IT band causes an electron transfer from Mo(IV) to Cu(II), producing a ferromagnetic mixed-valence isomer of Cu(I)Cu(II)[Mo(V)(CN)(8)].8H(2)O (Cu(I), S = 0; Cu(II), S = (1)/(2); Mo(V), S = (1)/(2)) (1'). 1' returns to 1 by irradiation of the reverse-IT band, which obeys the scheme for the potential energy surface in mixed-valence class II compounds.     

Second-harmonic spectroscopy of surface immobilized gold nanospheres above a gold surface supported by self-assembled monolayers

We have investigated linear and nonlinear optical properties of surface immobilized gold nanospheres (SIGNs) above a gold surface with a gap distance of a few nanometers. The nanogap was supported by amine or merocyanine terminated self-assembled monolayers (SAMs) of alkanethiolates. A large second-harmonic generation (SHG) was observed from the SIGN systems at localized surface plasmon resonance condition. The maximum enhancement factor of SHG intensity was found to be 3 x 10(5) for the SIGN system of nanospheres 100 nm in diameter with a gap distance of 0.8 nm. The corresponding susceptibility was estimated to be chi((2))=750 pmV (1.8 x 10(-6) esu). In the SIGN system supported with the merocyanine terminated SAMs, the SHG response was also resonant to the merocyanine in the nanogap. It was found that the SHG response of the SIGN systems is strongly frequency dependent. This leads us to conclude that the large chi((2)) is caused by enhanced electric fields at the localized surface plasmon resonance condition and is not due to an increase of the surface susceptibility following from the presence of the gold nanospheres. The observed SHG was consistent with the theoretical calculations involving Fresnel correction factors, based on the quasistatic approximation.     

Spontaneous membrane fusion induced by chemical formation of ceramides in a lipid bilayer

Mere chemical generation of ceramide and related double-chain lipids in the membrane of small unilamellar vesicles (SUVs) induces fusion of the vesicles. The lipids can be successfully prepared by dehydrocondensation between single-chain lipids (fatty acids and sphingosine or its analogues) in a lipid bilayer of the SUV by using a combination of 2-chloro-4,6-dimethoxy-1,3,5-triazine and amphiphilic tertiary amine catalysts, a process that can be compared to a successive enzyme model system for a fatty acyl-CoA synthetase followed by acyltransferase. The SUV spontaneously undergoes membrane fusion upon this internal chemical stimulation by the artificial enzyme system.     

Photodissociation of Mg+-XCH3 (X=F, Cl, Br, and I) complexes. II. Fragment angular and energy distributions

Angular and energy distributions of photofragments from Mg+-XCH3 (X=F, Cl, Br, and I) were deduced from time-of-flight (TOF) profiles measured by rotating the polarization direction of the dissociation laser with respect to ion beam direction. The TOF profiles of ICH3+ and MgI+ fragment ions produced from Mg+-ICH3 complex with 266 and 355 nm photons showed clear but opposite recoil anisotropy to each other. In addition, BrCH3+ formed by a dissociation of the Mg+-BrCH3 complex at a photolysis wavelength of 266 nm also showed an anisotropic distribution in the TOF profile which had the same behavior as the profile of ICH3+. For Mg+-FCH3 complex, CH3+ and MgF+ formed with a 266 nm photon had also spatial anisotropy, in which the TOF profile of MgF+ was almost opposite to that of MgI+. These anisotropic distributions were explained by (1) local excitation on the Mg+ ion, (2) rapid dissociation compared with a rotational period of the parent complex, and (3) geometrical structures of the parent complexes. Anisotropy beta parameter values were determined to be +1.30(ICH3+), -0.50(MgI+), +0.74(BrCH3+), and +0.75(CH3+ and MgF+). This dependence on the halogen atom observed in beta values was qualitatively explained by both the geometrical parameters and classical rotational periods of parent complexes. In the product energy distribution, 46%, 40%, 21%, 16%, and 16% of available energies were found to be transferred into translational energies of ICH3+, MgI+, BrCH3 +, CH3+, and MgF+, respectively. These values were compared with energy distributions estimated by a statistical prior distribution and a nonstatistical impulsive model. For ICH3+ and MgI+, the translational energies determined from the measurement had values between those estimated from statistical and nonstatistical models. On the other hand, the energy partitioning for the product ions of BrCH3+, CH3+, and MgF+ was found to be almost statistical. From these considerations, we concluded that nonstatistical processes were more important in the dissociation of Mg+-ICH3 than in other systems.     

Photodissociation of Mg+-XCH3 (X=F, Cl, Br, and I) complexes. I. Electronic spectra and dissociation pathways

Photodissociation spectra of Mg+-XCH3 (X=F, Cl, Br, and I) complexes have been measured in the ultraviolet region (225-415 nm). Several fragment ions with and without charge transfer (CT), Mg+, XCH3+, MgX+, MgCH3+, CH3+, and X+, were formed by evaporation (intermolecular bond dissociation) and intracluster reaction (intramolecular bond dissociation) via excited electronic states. Branching ratios of these ions were found to depend both on absorption bands and on halogen atoms. The ground states of the complexes were calculated to have geometries in which the Mg atom lies next to X atom of methyl halide molecules. Positive charges of the complexes are confirmed to be almost localized on Mg. Observed absorption bands were assigned to the transitions of the Mg+2P-2S atomic line perturbed by interactions with methyl halide molecules. Branching ratios of fragment ions can be partly explained by the stability of fragment ions and neutral counterparts. From the excited state potential energy curves along the Mg-X bond distance, dissociation reaction after CT was concluded to proceed predissociatively; potential curve crossings between the initially excited states and repulsive CT states may have a crucial role in the formation of CH3+, XCH3+, and X+. In particular, XCH3+ ions were formed via repulsive CT states having a character of electron excitation from Xnp to Mg+3s.     

Core-Excitation Three-Cluster Model of Borromean Nuclei

A new model of the core-nucleus and two-neutron system is introduced. The Faddeev equations of the ⁶He-n-n, ⁸He-n-n and ⁹Li-n-n systems for ⁸He, ¹⁰He and ¹¹Li are solved, respectively. The potential of the subsystem in the model has been constructed to make couplings of the ground state and the excited one inside the core-nucleus. Simple rank one separable Yamaguchi-type potentials between the core-nucleus and neutron are employed with the coupling strength determined from the energy levels and width. We solve the Faddeev three-cluster equations to obtain the low-lying energy levels of ⁸He, ¹⁰He and ¹¹Li. In order to understand the nuclear structures we calculate some inner wave functions and probabilities.     

Interfacial modification of organic photovoltaic devices by molecular self-organization

This feature article focuses on the relationship between the interfacial structures constructed by molecular self-organization and the properties of organic photovoltaic devices. The use of self-assembled monolayers (SAMs) is reviewed for metal and metal oxide/organic interfaces, while surface-segregated monolayers (SSMs) are introduced as a new method for the modification of organic/organic interfaces. Research up to now has clearly demonstrated the effectiveness of the control of energy levels and other properties at the interfaces to enhance photovoltaic performance. The possibility of more precise control of the interfacial structures is also discussed.     

Study on 1,3,5‐Triazine Chemistry in Dehydrocondensation: Gauche Effect on the Generation of Active Triazinylammonium Species

The reaction of 2‐chloro‐4,6‐dimethoxy‐1,3,5‐triazine (CDMT) with various nitrogen‐containing compounds, particularly tertiary amines (tert‐amines), has been studied for the preparation of 2‐(4,6‐dimethoxy‐1,3,5‐triazinyl)trialkylammonium salts [DMT‐Am(s)]. DMT‐Ams derived from aliphatic tert‐amines exhibited activity for the dehydrocondensation between a carboxylic acid and an amine to form an amide in a model reaction. Based on a conformational analysis of DMT‐Ams and tert‐amines by NMR and X‐ray diffraction methods, we concluded that a β‐alkyl group maintained in a gauche relationship with the nitrogen lone pair of tert‐amines significantly hinders the approach of CDMT to the nitrogen. Thus, trimethylamine and quinuclidine without such alkyl groups readily react with CDMT whereas triethylamine, possessing two or three such gauche β‐alkyl groups in the stable conformations, does not react at all. The theory of “gauche β‐alkyl group effect” proposed here provides useful guidelines for the preparation of DMT‐Ams possessing various tertiary amine moieties. An investigation of the dehydrocondensation activity of tert‐amines in a CDMT/tert‐amine system that involves in situ generation of DMT‐Am, showed that the gauche effect of the β‐alkyl group becomes quite pronounced; the yield of the amide decreases significantly with tert‐amines possessing an unavoidable gauche β‐alkyl group. Thus, the tert‐amine/CDMT systems are useful for judging whether tert‐amines can readily react with CDMT without isolation of DMT‐Ams.