We performed three-step sequential extraction experiments, with Milli-Q water, 1 M ammonium acetate solution and 0.11 M acetic acid as extractants of Cs, on soils radiologically contaminated by ...Fukushima Dai-ichi Nuclear Power Plant accident. Though aqueous solutions containing ammonium salts are effective to extract Cs from soils, the obtained overall extracted fractions of radioactive Cs by the three-step sequential extraction process were less than 30 %. Thus, the most of the radioactive Cs deposited on soils is probably incorporated in the non- or hardly exchangeable site of clay minerals, components of the soils.
The molecular geometries, electronic structures, and excitation energies of tin and lead phthalocyanine compounds, SnPc, PbPc, Sn(Pc)(2), and Pb(Pc)(2), were investigated using the B3LYP method ...within a framework of density functional theory (DFT). The geometries of SnPc, PbPc, Sn(Pc)(2), and Pb(Pc)(2) were optimized under C(4v), C(4v), D(4d), and D(4d) molecular symmetries, respectively. The excitation energies of these molecules were computed by the time-dependent DFT (TD-DFT) method. The calculated results for the excited states of three compounds other than the unknown Pb(Pc)(2) corresponded well with the experimental results of electronic absorption spectroscopy. The non-planar C(4v) molecular structure of SnPc and PbPc influences especially on the orbital energy of the HOMO-1 through mixing of the s-type atomic orbital of the central metal atom to the π system of the Pc ring in an anti-bonding way; however, the HOMO and the LUMO have little effect of the deviation from the planar structure because they have no contribution from the atomic orbital of the central metal. This orbital mixing pushes up the orbital energy of the HOMO-1, and reduces the energy of the metal-to-ligand charge transfer band of SnPc and PbPc. The calculated results also reproduced well the excitation profile of Sn(Pc)(2), which was quite different from that of SnPc. The strong interactions between the π-type orbitals of two Pc moieties altered the electronic structure resulting in the characteristic excitation profile of Sn(Pc)(2). In addition, this caused a reduction of about 0.8 eV in the ionization potential as compared to usual MPcs including SnPc, which was consistent with the experimental results.
In order to study the solid-state electronic structures for ground and excited states of tin phthalocyanine (SnPc), we extracted two types of dimers and a trimer as model systems from the crystal ...structure of the triclinic polymorph. One of the dimers had a convex configuration between two SnPc molecules, and the other took a concave one. The trimer consisted of both configurations. The molecular geometries, electronic structures, and excitation energies of the concave- and convex-type dimers and the trimer were investigated using the M06 method of the density functional theory (DFT). The geometries of these model systems were optimized under C sub(2h) molecular symmetry for the dimers and under C sub(1) for the trimer. The distances between two Sn atoms were optimized to be 6.805 and 6.374 Aa for concave- and convex-type dimers, respectively. The corresponding distances in the trimer were calculated to be 6.959 and 6.457 Aa, respectively. The Sn-Sn distances calculated for the dimers and trimer were consistent with the experimental values for the crystal. The energy diagrams of these model systems imply that each molecular orbital of an SnPc monomer forms the electron-energy band with a relatively large bandwidth due to strong intermolecular interactions in the solid state. The time-dependent DFT calculation for the trimer reproduced well the observed absorption spectrum in the solid state. It should be noted that a sum of the excited states calculated for the two types of the dimers reproduces the calculation results for the trimer well. From these results, it would be concluded that the electronic structure of SnPc for the solid state can be investigated by using these two dimers. The vertical values of the ionization potential (I sub(P)) were calculated with the optimized structures for the single molecule, two dimers and trimer of SnPc by the Delta SCF method. The first I sub(P)s decreased about 0.6 eV from monomer to trimer.
‘Early symptoms of schizophrenia’ (ESS) proposed by Nakayasu, are present during schizophrenic prodromal periods. Some of these symptoms can continue after the florid manifestation of the disease and ...the patients often experience them with ego‐alien feelings. Autochthonous experience, heightened awareness, and perception distortion (AHP) were selected from the list of ESS. The aim of this study was to confirm both prevalence and specificity of AHP in patients with schizophrenia as well as the relevance of the presence of AHP to symptomatology of schizophrenia. A structured interview was conducted to identify the presence of AHP in three groups of subjects; a schizophrenia group (Sc) with 37 patients, an affective disorder group (AD) with 27 patients, and a control group (NC) with 39 people. The prevalence of AHP was compared among the groups. Within the Sc, the relevance of AHP to Brief Psychiatric Rating Scale (BPRS) was assessed. AHP were present significantly more frequently in the Sc. The total scores for BPRS in the schizophrenic patients with AHP were significantly higher than in the patients without AHP. There was close correlation between AHP and BPRS items, with the degree of relevance depending on the form or perceptual domain. In conclusion, AHP were characteristic of patients with frank schizophrenia. To judge whether AHP were adequately specific to frank schizophrenia, further research of larger subjects is needed. Understanding the characteristics of AHP in patients with frank schizophrenia is important in the symptomatological evaluation of schizophrenia.
The molecular geometries, electronic structures, and excitation energies of tin and lead phthalocyanine compounds, SnPc, PbPc, Sn(Pc)
2
, and Pb(Pc)
2
, were investigated using the B3LYP method ...within a framework of density functional theory (DFT). The geometries of SnPc, PbPc, Sn(Pc)
2
, and Pb(Pc)
2
were optimized under
C
4v
,
C
4v
,
D
4d
, and
D
4d
molecular symmetries, respectively. The excitation energies of these molecules were computed by the time-dependent DFT (TD-DFT) method. The calculated results for the excited states of three compounds other than the unknown Pb(Pc)
2
corresponded well with the experimental results of electronic absorption spectroscopy. The non-planar
C
4v
molecular structure of SnPc and PbPc influences especially on the orbital energy of the HOMO−1 through mixing of the s-type atomic orbital of the central metal atom to the π system of the Pc ring in an anti-bonding way; however, the HOMO and the LUMO have little effect of the deviation from the planar structure because they have no contribution from the atomic orbital of the central metal. This orbital mixing pushes up the orbital energy of the HOMO−1, and reduces the energy of the metal-to-ligand charge transfer band of SnPc and PbPc. The calculated results also reproduced well the excitation profile of Sn(Pc)
2
, which was quite different from that of SnPc. The strong interactions between the π-type orbitals of two Pc moieties altered the electronic structure resulting in the characteristic excitation profile of Sn(Pc)
2
. In addition, this caused a reduction of about 0.8 eV in the ionization potential as compared to usual MPcs including SnPc, which was consistent with the experimental results.
The molecular geometries, electronic structures, excitation energies and ionization potentials of SnPc, PbPc, Sn(Pc)
2
and Pb(Pc)
2
, were investigated using the B3LYP method within a framework of the DFT method.
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