Adsorption of small molecules with the hydroxyl group on sodium halide cluster ions.

We have investigated adsorption of molecules with hydroxyl group, ROH, on sodium halide cluster ions, Na(n)X(n-1)(+) (X = F and I, n = 10-17) by mass spectrometry and by theoretical calculations. From analysis of the cluster ion intensities, the adsorption of one water molecule (R = H) is most efficient for Na(13)X(12)(+), whose structure has a NaX defect from a 3 x 3 x 3 cubic structure of n = 14. This result suggests that the defect has an important role in the adsorption reaction.

Infrared photodissociation spectroscopy of Al(+)(CH(3)OH)(n) (n = 1-4).

Infrared photodissociation spectra of Al(+)(CH(3)OH)(n) (n = 1-4) and Al(+)(CH(3)OH)(n)-Ar (n = 1-3) were measured in the OH stretching region, 3000-3800 cm(-1). For n = 1 and 2, sharp absorption bands were observed in the free OH stretching region, all of which were well reproduced by the spectra calculated for the solvated-type geometry with no hydrogen bond. For n = 3 and 4, there were broad vibrational bands in the energy region of hydrogen-bonded OH stretching vibrations, 3000-3500 cm(-1).

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+.

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.

Size-dependent structures of NanI+n-1 cluster ions with a methanol adsorbate: a combined study by photodissociation spectroscopy and density-functional theory calculation.

Methanol adsorption sites on NanI+n-1 ions were investigated. Photoexcitation to charge-transfer states of NanI+n-1 (methanol) predominantly produces two fragment ions: Nan-1I+n-2 (methanol) (neutral NaI loss) and Nan-1I+n-2(neutral NaI and methanol loss), without forming NanI+n-1 (methanol loss). The relative intensities of these fragments are correlated with the geometries and binding energies.

Multiple photofragmentation pathways with different recoil anisotropy from a metal-ion-ligand complex.

Spatial recoil anisotropy that is dependent upon the fragment-ion species is reported for the first time for a metal-ion-ligand complex after a single photoexcitation process by linearly polarized light. Upon excitation to the lowest three excited states of Mg+-ICH3, originating from the Mg+2P states, fragment ions of MgI+ and ICH+3 are found to have clear and different angular dependences, which are also characteristic of the excited states. These are explained from the results of theoretical work in that the calculated ground-state complex has a bent structure and further in that each transition dipole moment vector of the complex almost coincides with the Mg+ 3p orbital lobe direction in each case.