RESUMEN

Self-assemblies of anisotropic colloidal particles into colloidal liquid crystals and well-defined superlattices are of great interest for hierarchical nanofabrications that are applicable for various functional materials. Inorganic nanosheets obtained by exfoliation of layered crystals have been highlighted as the intriguing colloidal units; however, the size polydispersity of the nanosheets has been preventing precise design of the assembled structures and their functions. Here, we demonstrate that the anionic titanate nanosheets with monodisperse size reversibly form very unusual superstructured mesophases through finely tunable weak attractive interactions between the nanosheets. Transmission electron microscopy, polarizing optical microscopy, small-angle x-ray scattering, and confocal laser scanning microscopy clarified the reversible formation of the mesophases (columnar nanofibers, columnar nematic liquid crystals, and columnar nanofiber bundles) as controlled by counter cations, nanosheet concentration, solvent, and temperature.

RESUMEN

Infrared photodissociation of protonated water clusters with an Ar atom, namely H3O+-Ar and H+(H2O)2-Ar, was investigated by an imaging technique for mass-selected ions, to reveal the intra- and intermolecular vibrational dynamics. The presented system has the advantage of achieving fragment ion images with the cluster size- and mode-selective photoexcitation of each OH stretching vibration. Translational energy distributions of photofragments were obtained from the images upon the excitation of the bound (νb) and free (νf) OH stretching vibrations. The energy fractions in the translational motion were compared between νbI and νfI in H3O+-Ar or between νbII and νfII in H+(H2O)2-Ar, where the labels "I" and "II" represent H3O+-Ar and H+(H2O)2-Ar, respectively. In H3O+-Ar, the νfI excitation exhibited a smaller translational energy than νbI. This result can be explained by the higher vibrational energy of νfI, which enabled it to produce bending (ν4) excited H3O+ fragments that should be favored according to the energy-gap model. In contrast to H3O+-Ar, the νbII excitation of an Ar-tagged H2O subunit and the νfII excitation of an untagged H2O subunit resulted in very similar translational energy distributions in H+(H2O)2-Ar. The similar energy fractions independent of the excited H2O subunits suggested that the νbII and νfII excited states relaxed into a common intermediate state, in which the vibrational energy was delocalized within the H2O-H+-H2O moiety. However, the translational energy distributions for H+(H2O)2-Ar did not agree with a statistical dissociation model, which implied another aspect of the process, that is, Ar dissociation via incomplete energy randomization in the whole H+(H2O)2-Ar cluster.

RESUMEN

Ultraviolet photodissociation processes of gas phase Mg+-NO complex were studied by photofragment ion imaging experiments and theoretical calculations for excited electronic states. At 355 nm excitation, both Mg+ and NO+ photofragment ions were observed with positive anisotropy parameters, and theoretical calculations revealed that the two dissociation channels originate from an electronic transition from a bonding orbital consisting of Mg+ 3s and NO π* orbitals to an antibonding counterpart. For the NO+ channel, the photofragment image exhibited a high anisotropy (ß = 1.53 ± 0.07), and a relatively large fraction (∼40%) of the available energy was partitioned into translational energy. These observations are rationalized by proposing a rapid dissociation process on a repulsive potential energy surface correlated to the Mg(1S) + NO+(1Σ) dissociation limit. In contrast, for the Mg+ channel, the angular distribution was more isotropic (ß = 0.48 ± 0.03) and only ∼25% of the available energy was released into translational energy. The differences in the recoil distribution for these competing channels imply a reaction branching on the excited state surface. On the theoretical potential surface of the excited state, we found a deep well facilitating an isomerization from bent geometry in the Franck-Condon region to linear and/or T-shaped isomer. As a result, the Mg+ fragment was formed via the structural change followed by further relaxation to lower electronic states correlated to the Mg+(2S) + NO(2Π) exit channel.

RESUMEN

Vibrational predissociation processes of the H2O+Ar complex ion following mid-infrared excitations of the OH stretching modes and bending overtone of the H2O+ unit were studied by photofragment ion imaging. The anisotropy parameters, ß, of the angular distributions of the photofragment ions were clearly dependent on the type (branch) of rotational excitation, ß > 0 for the P-branch excitations, while ß < 0 for the Q-branch excitations, which were consistent with the previous theoretical predictions for the rotationally resolved optical transition of a prolate symmetric top. The translational energy distributions had a similar form, irrespective of the excitation modes. This result suggests that the prepared excited states underwent a common relaxation pathway via the bending or bending overtone state of the H2O+ unit. In addition, the available energy was preferentially distributed into the rotational energy of the H2O+ fragment ions rather than the translational energy. The mechanism of the rotational excitations of the H2O+ fragment ions was discussed based on the steric configuration of the H2O+ and Ar units at the moment of dissociation.

RESUMEN

Our recently developed trajectory surface hopping method uses numerical time derivatives of adiabatic potential gradients to estimate the nonadiabatic transition probability and the hopping direction. To demonstrate the practicality of the novel method, we applied it to the intermolecular photodissociation of a carbon dioxide dimer cation (CO2)2 +. Our simulations reproduced the measured velocity distribution of CO2 + fragments consisting of two (fast and slow) components and revealed that nonadiabatic transitions occur promptly toward the electronic ground state regardless of the fragment velocity. The structure of (CO2)2 + at optical excitation governs the fate of subsequent nonadiabatic dynamics leading to a fast or slow dissociation. Our method gave similar results to the fewest switches algorithm at lower computational expense. Our fast and robust surface hopping method is promising for the investigation of nonadiabatic dynamics in large and complex systems.

RESUMEN

Photochemistry of molecular complex ions in the atmosphere affects the composition, density, and growth of chemical species. Photodissociation processes of a mass-selected O2+(H2O) complex ion in the visible and ultraviolet regions were studied by ion imaging experiments and theoretical calculations. At 473 nm excitation, O2+ was the predominant photofragment ion produced. In this O2+ channel, the kinetic energy release was comparable to that estimated using a statistical dissociation model, and the anisotropy parameter was determined to be ß = 1.0 ± 0.1. On the other hand, the H2O+ photofragment ion was mainly produced at 355 nm excitation. The kinetic energy release for the H2O+ channel was large and nonstatistical, and the anisotropy parameter was ß = 1.9 ± 0.2. Theoretically, the 473 and 355 nm excitations were assigned to the B[combining tilde]2A''← X[combining tilde]2A'' and D[combining tilde]2A''← X[combining tilde]2A'' transitions, respectively, both of which were characterized by positive charge transfer from O2 to H2O subunits. To further investigate the dissociation mechanisms, potential energy curves (PECs) and surfaces (PESs) for the O2+(H2O) ion were calculated for the ground and excited states. As a result, the H2O+ channel at 355 nm excitation was explained by rapid dissociation on the repulsive PES of the D[combining tilde] state, while rapid electronic relaxation from the B[combining tilde] to X[combining tilde] state followed by dissociation in the ground state was inferred in the O2+ channel at 473 nm excitation.

RESUMEN

Velocity and angular distributions of photofragment CO2+ ions produced from mass-selected (CO2)2+ at 532 nm excitation were observed in an ion imaging experiment. The velocity distribution was assigned to two components, fast and slow velocity components, which was consistent with the previous study by Bowers et al. The anisotropy parameters of the angular distributions for the fast and slow velocity components were experimentally determined to be ßfast = 1.52 ± 0.14 and ßslow = 0.46 ± 0.10, respectively. In the theoretical approach, potential energy surfaces (PESs) of (CO2)2+ were calculated along two coordinates, the intermolecular distance and mutual orientations of the CO2 monomers. In addition, molecular dynamics simulations were performed. The visible transition of the most stable staggered structure of (CO2)2+ was attributed to C[combining tilde]2Ag ← X[combining tilde]2Bu by an excited state calculation. On the PES of the C[combining tilde] state, a potential well was found in which the two CO2 monomers lay side by side to each other, in addition to a repulsive slope along the intermolecular distance. The results of the simulations confirmed that the fragment CO2+ ions with fast velocity and large anisotropy originated from the rapid dissociation of (CO2)2+ on the repulsive slope. Meanwhile, the fragment CO2+ ions with slow velocity and small anisotropy were expected to emerge from statistical dissociation after large amplitude libration of CO2 molecules which was caused by the potential well in the excited state PES.

RESUMEN

An ion imaging apparatus with a double linear reflectron mass spectrometer has been developed, in order to measure velocity and angular distributions of mass-analyzed fragment ions produced by photodissociation of mass-selected gas phase complex ions. The 1st and the 2nd linear reflectrons were placed facing each other and controlled by high-voltage pulses in order to perform the mass-separation of precursor ions in the 1st reflectron and to observe the focused image of the photofragment ions in the 2nd reflectron. For this purpose, metal meshes were attached on all electrodes in the 1st reflectron, whereas the mesh was attached only on the last electrode in the 2nd reflectron. The performance of this apparatus was evaluated using imaging measurement of Ca+ photofragment ions from photodissociation reaction of Ca+Ar complex ions at 355 nm photoexcitation. The focused ion images were obtained experimentally with the double linear reflectron at the voltages of the reflection electrodes close to the predictions by ion trajectory simulations. The velocity and angular distributions of the produced Ca+ ([Ar] 4p1, 2P3/2) ion were analyzed from the observed images. The binding energy D0 of Ca+Ar in the ground state deduced in the present measurement was consistent with those determined theoretically and by spectroscopic measurements. The anisotropy parameter ß of the transition was evaluated for the first time by this instrument.

RESUMEN

An iron porphycene, a structural isomer of iron porphyrin, with trifluoromethyl groups at the peripheral position of the framework was incorporated into sperm whale apomyoglobin. The prepared myoglobin shows the higher O(2) affinity than the native protein. However, the oxygen affinity of the reconstituted myoglobin is lower than that of the myoglobin having an iron porphycene without trifluoromethyl groups, which is mainly originated from the enhancement of the O(2) dissociation. The CO affinity of the myoglobin with the trifluoromethylated iron porphycene is similar to that observed for the reference protein having the iron porphycene without trifluoromethyl groups, although their C-O stretching frequencies are significantly different. The relationship between the electronic states of the porphycene ring and the ligand bindings is discussed.

Asunto(s)

Monóxido de Carbono/metabolismo , Metamioglobina/metabolismo , Oxígeno/metabolismo , Porfirinas/química , Animales , Apoproteínas/metabolismo , Hierro/química , Ligandos , Metamioglobina/química , Mioglobina/metabolismo , Porfirinas/síntesis química , Cachalote

RESUMEN

The synthesis of the first fluorine-containing iron porphycenes, 2,7,12,17-tetraethyl-3,6,13,16-tetrakis(trifluoromethyl)porphycenatoiron(III) chloride [FePc(EtioCF(3))]Cl and its micro-oxo dimer [FePc(EtioCF(3))](2)O and their characterizations are reported. The crystal structure of [FePc(EtioCF(3))](2)O displays a severe saddled distortion of the porphycene framework due to the steric and electronic effects of the CF(3) substituents. The oxidation and reduction potentials for the micro-oxo dimer are significantly more positive compared to those observed for the reference micro-oxo dimer of the iron porphycenes and porphyrins having no electron-withdrawing substituent. Moreover, the (1)H and (19)F NMR spectra of [FePc(EtioCF(3))](2)O demonstrated that the micro-oxo dimer is readily converted into the monomeric ferrous complex in pyridine-d(5) through autoreduction for 1 day, although the reduction of the reference iron porphycenes and porphyrins are not observed in pyridine. These results indicate that the trifluoromethylated iron porphycene is a highly electron-deficient complex with a pyrrolic macrocycle ligand.

RESUMEN

[structure: see text] A pyrrolic macrocycle, beta-tetrakis(trifluoromethyl)porphycene, is the first example of a fluorine-containing porphycene. Four electron-withdrawing CF(3) substituents provide a highly distorted structure and an attractive electron-deficient nature for the porphycene framework. From the electrochemical study, it is found that the LUMO energy level for the beta-trifluoromethylporphycene is 1.24 V more stabilized compared to that for etioporphyrin. Moreover, the deprotonation of the inner N[bond]H proton in the porphycene was observed upon the addition of DBU.