Photothermal properties depend on the characteristics of energy transfer processes in solution. In this study, a time-resolved single beam thermal lens experiment in various solvents is employed to investigate the energy coupling effects which govern the energy transfer processes. Interestingly, it is observed that the behaviour of the photothermal propagation in solution depends on the property of solution and the concentration of solute in a single beam thermal lens configuration. These characteristics lead us to consider the solute-solvent coupling effects as well as the solvent-solvent interactions.

We have produced nanophase iron clusters inside a gas cell by decomposing iron pentacarbonyls from the mixture of ~20 Torr Fe(CO)5/~3 Torr SF6 with a pulsed CO2 laser. The product displayed a black tint. Its composition was identified to be mostly iron from an inductively coupled plasma (ICP) atomic emission spectrum. The X-ray diffraction (XRD) pattern indicates a body-centered cubic structure for the cluster. A transmission electron micrograph proves that their diameter ranges between 50 and 70 Å and their average diameter is 60 Å.

Tetradentate Schiff base ligands derived from 2-hydroxy-1-naphthaldehyde and aliphatic diamine have been synthesized. Cu(Ⅱ) complexes of Schiff base ligands have been synthesized from the free ligands and copper acetate. The mole ratio of ligand to copper was identified to be 1:1 by the result of elemental analysis and Cu(Ⅱ) complexes were in a four-coordinated configuration. The electrochemical redox process of Cu(Ⅱ) complexes in a DMF solution has been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry, and controlled potential coulometry. The redox process of Cu(Ⅱ) complexes is one electron transfer process in quasi-reversible and diffusion-controlled reaction. The electrochemical redox potentials and the kinetic parameters of Cu(Ⅱ) complexes are affected by the chelate ring of Schiff base ligands.

The steric effect on the first order hyperpolarizability of the β-nitrostyrene derivatives has been investigated by comparing the β values and the dihedral angles between the aryl and nitroalkenyl groups. In general the β value increased with the electron-donating ability of the substituent. The larger β value for 3,4-dimethoxy-β-nitrostyrene than that for p-methoxy-β-nitrostyrene has been attributed to the lower charge transfer energy for the former. The most striking substituent effect was observed in the β-methyl-β-nitrostyrene derivatives. Thus the β values for 3,4-dimethoxy- and p-methoxy derivatives of the latter decreased to near zero, probably because of the large distortion from planarity caused by the steric repulsion between the β-methyl and the aryl groups. The larger β value for p-dimethylamino-β-methyl-β-nitrostyrene has been interpreted with an increased electron-donating ability of the substituent and increased co-planarity.

Silicate and borosilicate gels were prepared by the sol-gel process and thermally treated in the 150-850 ℃ temperature range. Solid-state 1H MAS and 29Si CP/MAS NMR spectroscopy were used to investigate the effects of heat treatments on the silicate gel to glass conversion process. The 1H NMR isotropic chemical shifts and the relative intensities of hydrogen bonded and isolated silanol groups have been used to access the information concerning the dehydration process on the silicate gel surface. The 29Si NMR isotropic chemical shifts affected by the local silicon environment have been used to determine the degree of crosslinking, i.e. the number of siloxane bonds. These NMR results suggest that the silicate gel to glass conversion process is occurred by two stages which are dependent on the temperature; (1) the formation of particles up to 450 ℃ and (2) the formation of large particles by aggregation of each separated single particle above 450 ℃. In addition, the effects of B atom on the formation of borosiloxane bonds in borosilicates have been discussed.

We present the results of molecular dynamics simulations of monolayers of long-chain alkyl thiol [S(CH2)15CH3] molecules on an air-solid interface using the extended collapsed atom model for the chain-molecule and a gold surface for the solid surface. Several molecular dynamics simulations have been performed on monolayers with areas per molecule ranging from 18.30 to 32.10 Å2/molecule. It is found that there exist three possible transitions: a continuous transition characterized by a change in molecular configuration without change in lattice structure, a sudden transition characterized by the distinct lattice defects and perfect islands, and a third transition characterized by the appearance of a random, liquid-like state. The analysis of probability distributions of the segments shows that the structure of the chain-molecules at the air-solid interface is completely different from that at the air-water interface in the view of the degree of overlap of the probability distributions of the neighbor segments. The calculated diffusion coefficients of the chain-molecules on the monolayers seem to be not directly related to any one of the three transitions. However, the large diffusion of the molecules enhanced by the increment of the area per molecule may induce the second transition.

Growth and changes of electronically conducting polypyrrole (PPy) in the form of thin films polymerized on metal electrodes were investigated by electrochemical and in situ three-parameter ellipsometry methods at the wavelength of 632.8 nm. Although the optical equations produced multiple sets of solution, it was possible to determine a unique set of thickness and the optical constants of a film by auxiliary measurements and/or physical reasoning. The changes in the thickness and the optical properties of the polymers during polymerization and electrochemical oxidation/reduction was successfully followed by the three-parameter ellipsometric technique. The optical properties of the polymers continuously changed as the film grew. The imaginary part of the refractive index of polypyrrole seemed to be dominantly determined by the existence of an absorption band around the visible range.

Kinetic studies are carried out on the reactions of N-methyl-N-phenylcarbamoyl chlorides with benzylamines in acetonitrile. The selectivity parameters, ρX (=-0.6~-0.8), ρY (=1.0-1.1), and ρXY (=-0.14), suggest that the reaction proceeds by an SN2 mechanism. Kinetic isotope effects, kH/kD, involving deuterated nucleophiles (XC6H4CH2ND2) are all inverse type (<1.0), and the trends of changes in the magnitude are consistent with those expected for the observed negative sign of ρXY(=∂ρX/∂σY = ∂ρY/∂σX < 0). The relatively low activation enthalpies also support the proposed mechanism.

Thin films of polyaniline (PANI) salts were in situ deposited on a Pt plate during either chemical polymerization or electrochemical polymerization. The oxidation states of the salt films were controlled by the applied DC potential. AC impedance of the Pt/PANI electrode were measured in monomer-free 1 N HCl solution in order to investigate the electrodic properties of the films at the following applied DC potentials: 0, 0.45 and 0.75 V vs. SCE. Very small differences in film conductivity according to its oxidation state were observed by analysis of the impedance spectra, the reasons of which are complicated by enriched water content in the film and possible decrease in the film thickness during the measurements. The electrochemical activity of the film/solution interface varied with its oxidation state. Stability of the film in 1 N HCl solution was also evaluated by impedance and cyclic voltammetry measurements.

Catecholalane (1,3,2-Benzodioxaluminole, CA) prepared from catechol and aluminum hydride in tetrahydrofuran (THF) is found to be a selective reducing agent. The systematic study in order to characterize the reducing properties of the reagent under practical conditions (THF, 0 or 25 ℃, the quantitative amount of reagent to compound) has been done. The reagent reduces aldehydes, ketones, esters and acid chlorides to the corresponding alcohols, and primary amides to the corresponding amines. Especially noteworthy is that the reagent can convert both aromatic and aliphatic nitriles to the corresponding aldehydes in very high yields.

Reaction of carbonyl compounds with B-alkoxydiisopinocampheylborane (Ipc2BOR, R=H, Et, i-Pr, t-Bu) was investigated in detail in order to establish their usefulness as selective reducing agents. The reagents were extremely mild and reduced only aldehydes effectively under mild conditions. The reagents also reduced α,β-unsaturated aldehydes to the corresponding allylic alcohols without any detectable 1,4-reduction. Furthermore, aldehydes can be reduced in the presence of epoxides and acid chlorides. Consequently, the selective reduction of aldehyde groups in the presence of keto and all other functional groups has been realized with these reagents.

The layered perovskite oxide, KSr2Nb3O10, was synthesized. The interlayer potassium cations were readily exchanged by protons in hydrochloric acid solution to give the protonation compound, HSr2Nb3O10·0.5H2O. The intercalation compounds, [NH3(CH2)nNH3]xSr2Nb3O10, were also obtained by acid-base reactions between the protonation compound and organic bases, 1,n-alkyldiamines. The interlayer distances in the intercalation compounds were linearly increased with the increase of the number of carbon (Δc/Δn=1.05 Å) in 1,n-alkyldiamines. The intercalated alkyldiammonium ions formed a paraffin-like monolayer with average tilting angle (θ) of ca. 56°. The intercalation reactions occurred stoichiometrically. The thermal decomposition process of the intercalation compounds showed distinct three steps due to the desorption of hydrated water, the decomposition of organic moiety, and the decomposition of Sr-related compounds.

We present results of molecular dynamic (MD) simulations for the thermodynamic and structural properties of liquid n-alkanes, from n-butane to n-heptadecane, using three different models Ⅰ-Ⅲ. Two of the three classes of models are collapsed atomic models while the third class is an atomistically detailed model. Model Ⅰ is the original Ryckaert and Bellemans' collapsed atomic model [Discuss. Faraday Soc. 1978, 66, 95] and model Ⅱ is the expanded collapsed model which includes C-C bond stretching and C-C-C bond angle bending potentials in addition to Lennard-Jones and torsional potentials of model Ⅰ. In model Ⅲ all the carbon and hydrogen atoms in the monomeric units are represented explicitly for the alkane molecules. Excellent agreement of the results of our MD simulations of model Ⅰ for n-butane with those of Edberg et al.[J. Chem. Phys. 1986, 84, 6933], who used a different algorithm confirms the validity of our algorithms for MD simulations of model Ⅱ for 14 liquid n-alkanes and of models Ⅰ and Ⅲ for liquid n-butane, n-decane, and n-heptadecane. The thermodynamic and structural properties of models Ⅰ and Ⅱ are very similar to each other and the thermodynamic properties of model Ⅲ for the three n-alkanes are not much different from those of models Ⅰ and Ⅱ. However, the structural properties of model Ⅲ are very different from those of models Ⅰ and Ⅱ as observed by comparing the radial distribution functions, the average end-to-end distances and the root-mean-squared radii of gyrations.

Fluorescence from the electronically excited thiophosgene (Cl2CS) in its first excited singlet state (S1) is efficiently quenched by collision. Rates of the collision-induced electronic relaxation were obtained for various vibrational levels in the S1 state by measuring the fluorescence lifetimes. We found that the relaxation process is strongly energy-dependent; the rate consistently increases by a factor of ~40 with the increase of vibrational energy from 0 to 1450 cm-1. Collision-induced intersystem crossing from the S1 to the first triplet state (T1) is attributed to the major process responsible for the electronic relaxation.

The rotationally cooled but electronically excited m-xylyl radical has been generated in a jet from the gas mixture of precursor m-xylene and buffer gas He by a technique of corona excited supersonic expansion. The visible vibronic emission spectra in the transition of 12A2→12B2 of m-xylyl radical in the gas phase have been recorded using a Fourier transform spectrometer. The spectra have been analyzed for the assignments of the vibrational frequencies in the electronic ground state with combination of the torsional frequencies reported previously.

Ab initio Hartree-Fock and Becke 3-Lee-Yang-Parr (B3LYP) density functional theory calculations using 6-31G* basis set were carried out to study the vibrational spectra of anthracene neutral (h10 and d10) and radical cation (h10). We report results of the fundamental vibrational frequencies obtained on the basis of the calculations. The assignments of fundamentals show a one-to-one correspondence between the observed and calculated fundamentals.

The molecular geometry and vibrational frequencies of 9-fluorenone have been calculated using the Hartree-Fock and Becke-3-Lee-Yang-Parr(B3LYP) density functional methods with 6-31G* basis set. Harmonic vibrational frequencies obtained from the B3LYP calculation show good agreement with the available experimental data. A few vibrational fundamentals are newly assigned based on the B3LYP results. The B3LYP calculation is reconfirmed to be useful in the assignment of the fundamental vibrational frequencies.