Size-dependent reactivity of Rh cationic clusters to reduce NO by CO in the gas phase at high temperatures.

The reactivity of the reduction of NO pre-adsorbed on Rh2-9+ clusters by CO was investigated using a combination of an alternate on-off gas injection method and thermal desorption spectrometry. The reduction of RhnNxOy+ clusters by CO was evaluated by varying the CO concentration at T = 903 K. Among the RhnNxOx+ clusters, the Rh3N2O2+ cluster exhibited the highest reduction activity, whereas the other clusters, Rh2,4-9NxOx+, showed lower reactivity. Density functional theory (DFT) calculations for Rh3+ and Rh6+ revealed that the rate-determining step for NO reduction in the presence of CO was NO bond dissociation through the kinetics analysis using the RRKM theory. The reduction of Rh3N2O2+ is kinetically preferable to that of Rh6N2O2+. The DFT results were in qualitative agreement with the experimental results.

Hydrogen Storage Mechanism by Gas-Phase Vanadium Cluster Cations Revealed by Thermal Desorption Spectrometry.

The adsorption of hydrogen on gas-phase vanadium cluster cations, Vn+ (n = 3-14), at 300 K and desorption of hydrogen from hydride clusters, VnHm+, upon heating were observed experimentally by combined thermal desorption spectrometry and mass spectrometry analyses. The ratio m/n was approximately 1.3 for all n values at 300 K, which was reduced to approximately zero at 1000 K. For n = 4, stable cluster geometries of V4Hm+ (m = 0, 2, 4, and 6) were investigated by DFT calculations, revealing that V4 adopted a trigonal pyramidal structure and the H atoms adsorbed mainly on the µ2 bridge sites. The adsorption reaction pathway of one H2 molecule on V4+ was also investigated. The experimentally estimated desorption energies of the H2 molecules were consistent with their calculated binding energies. Among the observed hydride clusters, V6H8+ was found to be significantly thermally durable, probably because of its close-packed octahedral V6 core structure, with H atoms occupying all hollow sites.

Size-Dependent Geometrical Structures of Platinum Oxide Cluster Cations Studied by Ion Mobility-Mass Spectrometry.

Structures of platinum oxide cluster cations (PtnOm+) were studied by ion mobility-mass spectrometry in combination with theoretical calculations. Structures of oxygen-equivalent PtnOn+ (n = 3-7) clusters were discussed from the comparison between their collision cross sections (CCSs) obtained by mobility measurement and simulated CCSs of their structural candidates from structural optimization calculations. Assigned structures of PtnOn+ were found to be composed of Pt frameworks and bridging O atoms, which follows the previous theoretical prediction on the neutral clusters. The structures change from planar (n = 3 and 4) to three-dimensional (n = 5-7) with increasing cluster size by deforming platinum frameworks. Comparison with other group-10 metal oxide cluster cations (MnOn+; M = Ni and Pd) showed that the PtnOn+ structures have a similar tendency to PdnOn+ rather than NinOn+.

Structural assignments of yttrium oxide cluster cations studied by ion mobility mass spectrometry.

The geometric structures of yttrium oxide cluster ions, YnOm+ (n = 3-11), were experimentally assigned for stable compositions by ion mobility mass spectrometry combined with theoretical calculations. The stable compositions were firstly determined by collision induced dissociation experiments in mass spectrometry as YO(Y2O3)x+ and YO2(Y2O3)x+ for odd numbers of Y atoms (n = 2x + 1) and (Y2O3)x+ and O(Y2O3)x+ for even numbers of Y atoms (n = 2x). The structures of the ions with the above compositions were assigned by comparing the collision cross sections obtained in the ion mobility measurement with those obtained by theoretical calculations. The assigned structures have the following two characteristic features. Firstly, metal-metal or oxygen-oxygen bonds were rarely observed, and most of the oxygen atoms bridge two Y atoms, which is due to the ionic bonding nature between Y3+ and O2- ions. Secondly, common Y-atom frameworks were obtained for the ions with the same number of Y atoms n. For example, for the clusters with even numbers of Y atoms, one atomic oxygen radical anion (O-) in the most stable structures of (Y2O3)x+ was replaced with a superoxide ion (O2-) to form the most stable structures of O(Y2O3)x+ ions, keeping the Y-atom framework geometries.

Geometrical Structures of Gas-Phase Cerium Oxide Cluster Cations after Reaction with Nitric Oxide Studied by Ion Mobility Mass Spectrometry.

Cerium oxide cluster cations were reacted with nitric oxide molecules and then measured by ion mobility mass spectrometry (IMMS). CenO2n+1N+ species appeared as products of the reaction CenO2n+ + NO → CenO2n+1N+, and their collision cross sections (CCSs) with helium were obtained by IMMS. The experimental CCSs of CenO2n+1N+ were 2-6 Å2 larger than those of CenO2n+ for n = 4-10. Geometrical structures of Ce4O9N+ and Ce5O11N+ were assigned by comparing experimental CCSs with theoretically calculated CCSs of candidate structures. The suggested structures showed that the adsorbed NO molecule is oxidized by the CenO2n+ cluster into a nitrite (NO2-) or nitrate (NO3-). The CenO2n+1N+ species are regarded as intermediates of the NO oxidation reaction CenO2n+ + NO → CenO2n-1+ + NO2, and therefore, the present results are helpful for understanding redox reactions involving gas-phase CenO2n+ cluster ions.

Decomposition of nitric oxide by rhodium cluster cations at high temperatures.

Decomposition reactions of NO molecules on gas-phase Rhn+ (n = 6-9) clusters were investigated by gas-phase thermal desorption spectrometry and density functional theory calculations. We found that NO adsorbs on the clusters, forming RhnNxOx+ at room temperature. Upon heating, NO desorption was observed below 800 K. Above 800 K, while for n = 7 and 8, each of Rh7N3O3+, Rh7N4O4+, and Rh8N3O3+ was found to release an N2 molecule, no N2 formation was clearly observed for Rh6,9NxOy+. We considered that both Rh7N3O3+ and Rh8N3O3+ have at least two dissociated NO molecules, while Rh6NxOx+ (x = 1-3) has one or less. Our computational results for Rh8N3O3+ suggested that the formation of an N-N bond in the Rh8N3O3+ structure must overcome an energy barrier of ∼2 eV, which is the highest among the suggested possible reaction pathways. These findings suggested that the size-dependent activity of NO decomposition is governed primarily by how NO molecules are adsorbed on Rhn+ clusters, i.e. whether two or more N atoms from dissociated NO molecules exist in the NO adsorbed clusters, and secondly, by the readiness of the N-N bond formation.

Sequential growth of iridium cluster anions based on simple cubic packing.

Geometric structures of free iridium cluster anions, Irn-, were examined by means of ion mobility mass spectrometry and density functional theory calculation for n = 3-15 with the additional help of photoelectron spectroscopy for n = 4-10. It has been revealed that Irn- clusters with n ≥ 5 favor a square facet and take a cubic motif in contrast to the face-centered cubic structures in the corresponding nanoparticles and bulk. A growth sequence of Irn- for n = 5-15 is proposed: single Ir atoms are sequentially attached to one side of the square plane of Ir4- to form a cubic Ir8-, and are then continuously attached on one of the square facets of Ir8- for n = 9-12 and Ir12- for n = 13-15.

Oxygen Release from Cationic Niobium-Vanadium Oxide Clusters, NbnVmOk+, Revealed by Gas Phase Thermal Desorption Spectrometry and Density Functional Theory Calculations.

Thermal dissociation of the cationic niobium-vanadium oxide clusters, NbnVmOk+ (n + m = 2-8), was investigated by gas phase thermal desorption spectrometry. The oxygen-rich NbnVmOk+ released O and O2 for odd and even values of n + m, respectively. Substitution of more than one Nb atom in NbnOk+ by V drastically lowered the desorption temperature of O2 for even values of n + m, whereas the substitution of more than two Nb atoms opened a new desorption path involving the release of O2 for odd values of n + m. The substitution effects can be explained by the fact that Nb atoms display the +5 state, whereas V atoms can exist in either the +4 or +5 states. The geometrical structures of selected NbnVmOk+ clusters were optimized and the energetics of the release of O/O2 from the clusters was discussed on the basis of the results of DFT calculations.

Desorption of Oxygen from Cationic Niobium Oxide Clusters Revealed by Gas Phase Thermal Desorption Spectrometry and Density Functional Theory Calculations.

Thermal dissociation of cationic niobium oxide clusters (NbnOm+) was investigated by gas phase thermal desorption spectrometry. The dominant species formed at 300 K were NbnO(5/2)n+p+ (n = 2, 4, 6, ...; p = 0, 1, 2, ...) and NbnO((5/2)n-1/2)+q+ (n = 3, 5, ...; q = 0, 1, 2, ...). At higher temperatures, the more oxygen-rich clusters were observed to release O2. However, the desorption of O2 from NbnOm+ was found to be insignificant in comparison with VnOm+ because Nb tends to have a +5 oxidation state exclusively, whereas V can have both +4 and +5 oxidation states. The propensity for the release of O atoms was manifested in the formation of NbnO(5/2)n-1/2+ from NbnO((5/2)n-1/2)+1+ for odd values of n, whereas VnO((5/2)n-1/2)+1+ released O2 molecules instead. The energetics of the O and O2 release from the Nb and V oxide clusters, respectively, was consistent with the results of DFT calculations.

Geometrical Structures of Partially Oxidized Rhodium Cluster Cations, Rh6Om+ (m = 4, 5, 6), Revealed by Infrared Multiple Photon Dissociation Spectroscopy.

Infrared multiple photon dissociation (IRMPD) spectra of Rh6Om+ (m = 4-10) are obtained in the 300-1000 cm-1 spectral range using the free electron laser for infrared experiments (FELIX) via dissociation of Rh6Om+ or Rh6Om+-Ar complexes. The spectra are compared with the calculated spectra of several stable geometries obtained by density functional theory (DFT) structural optimization. The spectrum for Rh6O4+ shows prominent bands at 620 and 690 cm-1 and is assigned to a capped-square pyramidal Rh atom geometry with three bridging O atoms and one O atom in a hollow site. Rh6O5+ displays bands at 460, 630, 690, and 860 cm-1 and has a prismatic Rh geometry with three bridging O atoms and two O atoms in a hollow site. Rh6O6+ shows three intense bands around 600-750 cm-1 and multiple weak bands in the range of 350-550 cm-1. This species has a prismatic Rh geometry with four bridging O atoms and two O atoms in a hollow site. Considering that Rh6Om+ (m ≤ 3) adopts tetragonal bipyramidal Rh6 structures, the change at m = 4 to capped bipyramidal and at m = 5 to prismatic geometries results in a reduction of the number of triangular hollow sites. Since NO preferentially binds on a triangular hollow site through the N atom, the geometry change lowers the possibility of NO dissociative adsorption.

Gold Atoms Supported on Gas-Phase Cerium Oxide Cluster Ions: Stable Stoichiometry and Reactivity with CO.

The stability and reactivity of cationic gold-cerium oxide clusters, AumCenO2n+x+ (m ≤ 4, n ≤ 7, -1 ≤ x ≤ 2), were examined experimentally and computationally. These clusters were generated by simultaneous laser ablation of gold and cerium oxide targets and analyzed by time-of-flight mass spectrometry combined with gas-phase temperature-programmed desorption. Stable compositions of gold-cerium oxide clusters were identified as AumCenO2n+ and AumCenO2n+1+ for m ≥ 1, containing one oxygen atom more than the stable gold-free cerium oxide clusters CenO2n-1+ and CenO2n+. In either case, the stable clusters mainly consisted of Ce4+ and O2-, and the gold atoms had an oxidation state of +1. The reactivity of cerium oxide clusters toward CO was modified by gold atoms, which hindered CO oxidation while efficiently promoting its adsorption. According to density functional theory calculations, the oxygen-centered radical of cerium oxide clusters, considered to be the reactive site, was geometrically and electronically inactivated by gold atoms, which functioned as a CO adsorption site.

Oxidation of Nitric Oxide on Gas-Phase Cerium Oxide Clusters via Reactant Adsorption and Product Desorption Processes.

The reactivity of cerium oxide cluster cations, CenO2n+x(+) (n = 2-9, x = -1 to +2), with NO was investigated using gas-phase temperature-programmed desorption (TPD) combined with mass spectrometry. Target clusters were prepared in the gas phase via the laser ablation of a cerium oxide rod in the presence of oxygen, which was diluted using helium as a carrier gas. NO adsorbed onto stoichiometric and oxygen-rich clusters of CenO2n+x(+) (x = 0-2), forming CenO2n+x(NO)(+) (x = 0-2) species. Gas-phase TPD was measured for the NO-adsorbed clusters, revealing that CenO2n(NO)(+) released NO2 at 600-900 K, forming CenO2n-1(+). Therefore, the overall reaction was the oxidation of NO by the CenO2n(+) clusters, which was explained in terms of a Langmuir-Hinshelwood type reaction. An activation barrier existed between the initial complex (CenO2n(NO)(+)) and the final oxidation products (CenO2n-1(+) + NO2). To determine the nature of the intermediates and the activation barrier, TPD was also performed on CenO2n-1(NO2)(+), which had been prepared through the adsorption of NO2 on CenO2n-1(+) for comparison. The activation barrier was associated with the release of NO2 from the intermediate complex (CenO2n-1(+)-NO2 → CenO2n-1(+) + NO2) rather than the structural rearrangement that formed NO2 in the other intermediate complex (CenO2n(+)-NO → CenO2n-1(+)-NO2).

Reactivity of oxygen deficient cerium oxide clusters with small gaseous molecules.

Oxygen deficient cerium oxide cluster ions, Ce(n)O(m)(+) (n = 2-10, m = 1-2n) were prepared in the gas phase by laser ablation of a cerium oxide rod. The reactivity of the cluster ions was investigated using mass spectrometry, finding that oxygen deficient clusters are able to extract oxygen atoms from CO, CO2, NO, N2O, and O2 in the gas phase. The oxygen transfer reaction is explained in terms of the energy balance between the bond dissociation energy of an oxygen containing molecule and the oxygen affinity of the oxygen-deficient cerium oxide clusters, which is supported by DFT calculations. The reverse reaction, i.e., formation of the oxygen deficient cluster ions from the stoichiometric ones was also examined. It was found that intensive heating of the stoichiometric clusters results in formation of oxygen deficient clusters via Ce(n)O(2n)(+) → Ce(n)O(2n-2)(+) + O2, which was found to occur at different temperatures depending on cluster size, n.

Stable stoichiometry of gas-phase cerium oxide cluster ions and their reactions with CO.

Cerium oxide cluster ions, Ce(n)O(2n+x)(+) (n = 2-9, x = -1 to +2), were prepared in the gas phase by laser ablation of a cerium oxide rod in the presence of oxygen diluted in He as the carrier gas. The stable stoichiometry of the cluster ions was investigated using a mass spectrometer in combination with a newly developed post heating device. The oxygen-rich clusters, Ce(n)O(2n+x)(+) (x = 1, 2), were found to release oxygen molecules, and Ce(n)O(2n+x)(+) (x = -1, 0) were exclusively formed by post heating treatment at 573 K. The Ce(n)O(2n-1)(+) and Ce(n)O(2n)(+) clusters were found to be thermally stable, and the oxygen-rich clusters consisted of robust Ce(n)O(2n-1)(+) and Ce(n)O(2n)(+) and weakly bound oxygen atoms. Evaluation of the reactivity of Ce(n)O(2n+x)(+) with CO molecules demonstrated that Ce(n)O(2n)(+) oxidized CO to form Ce(n)O(2n-1)(+) and CO2, and the rate constants of the reaction were in the range of 10(-12)-10(-16) cm(3) s(-1). The CO oxidation reaction was distinct for n = 5, which occurred in parallel with the CO attachment reaction.

Text messaging: are dependency and Excessive Use discretely different for Japanese university students?

Text messaging may be excessive and young people may be dependent on it. We distributed the Self-perception of Text-message Dependency Scale (STDS), Hospital Anxiety and Depression Scale (HADS), Temperament and Character Inventory (TCI), and Relationship Questionnaire (RQ) to 223 Japanese university students in a two-wave study, separated by a 5-month interval. The STDS yielded a three-factor structure. The STDS scores across the two measurement occasions were stable across time (except for the Relationship Maintenance subscale). A hierarchical cluster analysis suggested a three-class structure interpreted as Normal Users, Excessive Users, and Dependent Users. Excessive Users and Dependent Users were characterized by a young age at initial mobile phone use, more frequent use of text messaging, higher Novelty Seeking, and better Other-Model patterns of adult attachment. Unlike Excessive Users, Dependent Users were characterized by lower Self-directedness, poorer Self-Model of adult attachment, and higher anxiety and depression. The Excessive Users, but not the Dependent Users, were characterized by high Reward Dependence and Co-operativeness. The present study demonstrated that the STDS has a robust factor structure, good construct validity, and temporal stability (except for Relationship Maintenance subscale); students could be classified into normal, excessive, and Dependent Users of the text messaging; and Dependent Users were characterized by Excessive Use and personality immaturity.

Do people cope with situations as they say? Relationship between perceived coping style and actual coping response.

AIM: The coping style that individuals think they will use when encountering stressful situations may differ from actual coping response in real situations. METHODS: In a longitudinal study on some 500 university students, perceived coping style was identified using the Coping Inventory for Stressful Situations on the first occasion. In the subsequent eight test occasions, which occurred on a weekly basis, the students were asked about a negative life event that occurred during the past week and the actual coping responses they used. RESULTS: The perceived coping style and the actual coping response matched well for task-oriented and emotion-oriented coping. For avoidance-oriented coping, however, perceived coping style and actual coping response were weakly correlated. CONCLUSION: Epidemiological studies on coping and mental health should discriminate coping style and coping response. Clinicians should be cautious about patients' own information about avoidance-oriented coping.

Effects of temperament and character profiles on state and trait depression and anxiety: a prospective study of a Japanese youth population.

Objective. To examine the effects of temperament and character profiles on state and trait depression and anxiety in a Japanese youth population. Method. Japanese university students were solicited for participation in a two-wave study, with assessments performed at Time 1 (T1) and Time 2 (T2), separated by a five-month interval. A total of 184 students completed the Japanese version of the temperament and character inventory (TCI) at T1 and the Hospital Anxiety and Depression Scale (HADS) at T1 and T2. We posited two latent variables, trait depression and anxiety, composed of the T1 and T2 HADS depression and anxiety scores, respectively. We also posited that temperament domain traits would predict character domain traits, and that all the personality traits would be linked to trait depression and anxiety and also predict T2 depression and anxiety. Results. Structural regression modeling showed that (1) only high Novelty Seeking predicted T2 Anxiety score, (2) trait depression and anxiety were linked to high harm avoidance and low self-directedness, and (3) trait depression was linked to high self-transcendence whereas trait anxiety was linked to low reward dependence, persistence, and cooperativeness. Conclusion. The characteristic associations between TCI subscales and depression and anxiety were limited to the trait rather than state aspects of depression and anxiety.

Narcissism: its function in modulating self-conscious emotions.

This study focused on the functional aspects of narcissism in regulating self-conscious emotions (guilt, shame, hubristic pride, and achievement-oriented pride) as well as two other attribution styles (externalization and detachment). The authors investigated Japanese university students (N = 452) with regard to their self-conscious emotions using the Test of Self-Conscious Affect-3 (TOSCA-3) and their narcissistic personality using the short version of Narcissistic Personality Inventory (NPI-S). Structural equation modeling was used for the analysis. The authors found that narcissism led individuals to feel achievement-oriented pride, hubristic pride, externalization, and detachment, but inhibited feelings of shame. It did not have a significant effect on guilt. Shame-proneness prompted hubristic pride and externalization. Guilt-proneness inclined an individual toward achievement-oriented pride, but deterred externalization. In this article, the authors present and interpret these results in detail and then discuss how they can be utilized in psychotherapy.

Self-conscious affects: their adaptive Functions and relationship to depressive mood.

This study used a structural equation model to examine the influence of resilience on the four self-conscious affects (guilt-proneness, shame-proneness, externalization, and detachment) assessed in the Test of Self-Conscious Affect-3 (TOSCA-3) and their impact on depressive mood. Our subject population consisted of 447 Japanese university students. The first analysis explored which TOSCA-3 affects help an individual adapt to stressful situations. The concept of "resilience" was used as an indicator to evaluate the adaptive functions. We based this on the assumption that an individual with higher resilience is able to use more adaptive affects. In the second analysis, taking the above relationship between resilience and the self-conscious affects into consideration, we examined how those variables as well as a negative life event are related to depressive mood. To assess the resilience level and depressive mood, we adopted the Resilience Scale (RS) and Self-rating Depressive Scale (SDS), respectively. The first analysis showed that the more resilient an individual was, the more prone they were to "detachment" and the less "shame" they experienced. The level of resilience did not have a significant effect on "guilt" or "externalization." In the second analysis we found that "resilience" had a direct inverse effect on depressive mood that was also mediated by "shame" and "detachment." We discuss how the particular self-conscious affects comprising each adaptive function are related to depressive mood.

Effects of child abuse history on borderline personality traits, negative life events, and depression: a study among a university student population in Japan.

To simultaneously examine the impact of childhood abuse history on borderline personality traits, negative life events, and depression, undergraduate students (N=243) were studied by questionnaire surveys with one week intervals. Neglect and emotional abuse as well as sexual maltreatment predicted borderline personality traits and baseline depression. Baseline depression as well as the impact of negative life events occurring the week prior predicted depression a week later. However, after considering the baseline depression level, child abuse history failed to predict the follow-up depression level. Borderline personality traits did not moderate these findings. Childhood emotional and sexual abuse history may influence depression and borderline personality traits.