The chemical reactivity of 5,7-dimethoxycoumarine with adenosine has been calculated by the frontier electron and PPP-Cl MO methods. Results suggest that the major reactivity of the 5,7-dimethoxycoumarin is highest at the carbon-4 (position 4), whereas the electrophilic reactivity is generally spread all over the 5,7-dimethoxycoumarin molecule. These results are consistent with the experimental photoaddition reaction products. The small change of bond orders on excitation does not give enough reactivity to triplet states or the efficient intersystem crossing from $T_1\;to\;S_0$ inhibits photoaddition of 5,7-dimethoxycoumarine to adenosine. Although the relative intensity of the singlet band appears to be considerably higher than the triplet band intensity, its integrated intensity, i.e. oscillator strength, is comparable to that of the 5,7-dimethoxycoumarin and adenosine bands.

The lowest excited state of styrylquinoxaline (StQx) has been studied by the SCF-MO-CI P-P-P and MM2 method. Results suggest that the lowest excited state is of a ${\pi},{\pi}^{\ast}(S_1$) nature with the n,${\pi}^{\ast}(S_2)$ state lying slightly above it. On the basis of these calculations the observed electronic spectra are discussed. The calculated absorption spectra are qualitatively similar to experimental ones with their characteristic visible bands. MM2 force field calculation suggested that the postulated conformers are different from each other in energy and planarity and are seperated by a barrier of about 4 Kcal/mole.

The crystal structure of $Ag^+$-exchanged zeolite A vacuum-dehydrated at $370^{\circ}C$ and then treated with carbon monoxide at $$23^{\circ}C$ has been determined by single crystal x-ray diffraction methods in the cubic space group Pm3m at $23^(1){\circ}C$ ; a = 12.116 (2)${\AA}$. The structure was refined to the final error indices $R_1\;=\;0.061\;and\;R_2$(weighted) = 0.068 using 349 independent reflections for which I > 3${\sigma}(I).\;3.6\;Ag_+-CO$ complexes, where -CO may represent -CHO or -$CH_2OH$, were found in each large cavity. By coordination to silver atoms followed by reaction with $Ag^{\circ}and\;H^+$ within the zeolite, carbon monoxide has been partially reduced. In about 28% of the sodalite units, a $Ag_6(Ag^+)_2$ cluster may be present. In about 37% of the sodalite units, three $Ag^+$ ions are found on threefold axes where they may be bridged by three water molecules. The remaining 35% of the sodalite units are empty of silver species. Two $Ag^+$ ions per unit cell are associated with 8-ring oxygens. The remaining ca $$3Ag^+$ ions per unit cell have been reduced during the synthesis and have migrated to form small silver crystallities on the surface of the zeolite single crystal.

The crystal structure of partially $Ag^+$-exchanged zeolite A, $Ag_{3.2}Na_{8.8}$-A, vacuum dehydrated at $360^{\circ}C$ and then exposed to 0.1 torr of cesium vapor for 12 hours at $250^{\circ}C$ has been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m (a = 12.262(2)${\AA})\;at\;21(1)^{\circ}C$. The structure was refined to the final error indexes $R_1=0.068\;and\;R_2=0.072$ by using 338 reflections for which $I_o\;>\;3{\sigma}(I_o)$ and the composition of unit cell is $Ag_{3.2}Cs_{8.8}-A.\;3\;Cs^+$ ions lie on the centers of the 8-rings at sites of D4h symmetry. Two crystallographycally different 6-ring $Cs^+$ ions were found: 1.5 $Cs^+$ ions at Cs(2) are located inside of sodalite cavity and 4.3 $Cs^+$ ions at Cs(3) are located in the large cavity. The fractional occupancies observed at Cs(2) and Cs(3) indicate that the existence of at least three types of unit cells with regard to the 6-ring $Cs^+$ ions. For example, 50% of unit cells may have two $Cs^+$ ions at Cs(2) and 4 $Cs^+$ ions at Cs(3). 30% of unit cells may have one Cs+ ion at Cs(2) and 5 $Cs^+$ ions at Cs(3). The remaining 20% would have one $Cs^+$ ion at Cs(2) and 4 $Cs^+$ ions at Cs(3). On threefold axes of the unit cell two non-equivalent Ag atom positions are found in the large cavity, each containing 0.64 and 1.92 Ag atoms, respectively. A crystallographic analysis may be interpreted to indicate that 0.64 $(Ag_5)^+$ clusters are present in each large cavity. This cluster may be viewed as a tetrasilver molecule $(Ag_4)^0$(bond length, 2.84${\AA}$) stabilized by the coordination of one $Ag^+$ ion.

The relations between the repulsive interactions and the electron density overlaps are investigated for various closed shell-closed shell pairs, including the systems containing alkali and halide ions. It is found that the repulsive interaction($V_{rep}$) depends on the overlap of the electron density($S_{\rho}$) according to a simple exponential relation, $V_{rep}$ = $As_{\rho}\;^{\alpha}$. Furthermore, for most of the closed shell systems the $\alpha$ values are near unity and the A values do not vary much. The same tests are also performed for the open shell-closed shell, and the open shell-open shell pairs. Although the results for these systems also show exponential dependences of the repulsive interactions on the density overlaps, the details of the dependence differ greatly from those for the closed shell systems and also vary widely from one individual system to another.

Two crystal structures of dehydrated $Ag^+\;and\;Ca^{2+}$ exchanged zeolite A, $Ag_2Ca_$5-A, reacting with 0.01 Torr of Cs vapor at $200^{\circ}C$ for 2 hours and 0.1 Torr of Cs vapor at $250^{\circ}C$ for 48 hours, respectively, have been determined by single crystal X-ray diffraction techniques. Their structures were solved and refined in the cubic space group Pm3m at $21(1)^{\circ}C$. The stoichiometry of first crystal was $Ag_2Ca_5$-A (a = 12.294(1)${\AA}$), indicating that Cs vapor did not react with cations in zeolite A and that of second crystal was $Ag_2Cs_{10}$-A (a = 12.166(1)${\AA}$), indicating that all $Ca^{2+}$ ions were reduced by Cs vapor and replaced by $Cs^+$ ions. Full-matrix least-squares refinements of $Ag_2Ca_5-A\;and\;Ag_2Cs_{10}$-A has converged to the final error indices, $R_1\;=\;0.041\;and\;R_2$ = 0.048 with 227 reflections, and $R_1\;=\;0.117\;an\;n\;fdd\;R_2$ = 0.120 with 167 reflections, respectively, for which I > $3{\sigma}$(I). In the structure of $Ag_2Ca_5$-A, both $Ag^+$ ions and $Ca^{2+}$ ions lie on two crystal symmetrically independent threefold axis sites on the 6-rings; $2\;Ag^+$ ions are recessed 0.33 ${\;AA}$ from the (111) planes of three O(3) oxygens and 5 $Ca^{2+}$ ions lie on the nearly center of each 6-oxygen planes. In the structure of $Ag_2Cs_{10}-A,\;Cs^+$ ions lie on the 5 different crystallographic sites. 3 $Cs^+$ ions lie at the centers of the 8-rings at sites of D4h symmetry. 6 $Cs^+$ ions lie on the threefold axes of unit cell: $4\;Cs^+$ ions are found deep in the large cavity and 2 $Cs^+$ ions are found in the sodalite cavity. One $Cs^+$ ion is found in the large cavity near a 4-ring.

The molecular structure of cyclobutylmethyl ketone (c-$C_4H_7COCH_3$) has been investigated by molecular mechanics II (MM2). For the monosubstituted cyclobutane there are two possible ring conformations, the equatorial and axial form, but for the cyclobutylmethyl ketone the equatorial form is predominant conformation. For the $COCH_3$ moiety there are two stable orientations which are the equatorial-gauche and the equatorial-trans form. The equatorial-gauche form where the C = O bond is nearly eclipsing (torsional angle ${\angle}C4-C3-C2-O10=14.5^{\circ}$) one of the ${\alpha}$C-C bonds of the four-membered ring was preferred conformer with steric energy of 13.37 kcal/mol. The equatorial-trans form where the C = O bond is nearly eclipsing (${\angle}C4-C3-C2-O10=145.0^{\circ}$) the ${\alpha}$ C-H bond of the four-membered ring was less stable conformer with steric energy of 15.40 kcal/mol.

A kinetic study on the chemiluminescence resulting from the reaction between bis(2,4-dinitrophenyl) oxalate(DNPO) and hydrogen peroxide in the presence of fluorescent polycyclic aromatic hydrocarbons in a viscous phthalate medium has been conducted. The resultant data confirm that the reaction between DNPO and $H_2O_2$ is the rate determining step. Higher rate constants are obtained with DNPO than those with bis(2,4,6-trichlorophenyl) oxalate (TCPO).

Adsorption of 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, and 1,6-hexanedithiol on silver surface has been investigated by surface-enhanced Raman spectroscopy. It has been found that the conformations of the adsorbates were mainly affected by steric interaction of the adsorbates with the surface. As the alkyl chain length separating the thiol groups increased, surface stacking efficiency became increasingly important in determining conformation of the adsorbate on the surface.

The electrochemical behaviors of 4-(2)-thiazolylazo)-resorcinol (TAR) in acetonitrile solution was studied by DC polarography, cyclic voltammetry, controlled-potential coulometry and UV-Vis spectroscopy. The electrochemical reduction of TAR occurs in four-one electron reduction steps in acetonitrile solution. The products of the first and the third electron transfer are speculated to be a relatively stable anion radical. The second electron transfer to the dianion is followed by a chemical reaction producing a protonated species. The product of the fourth electron transfer also produces the corresponding amine compounds with a following reaction. Also every reduction wave was diffusion controlled. The first reduction wave is considerably reversible and the other waves are less reversible.

The gas phase thermal decomposition of 1-bromo-3-chloropropane in the presence of radical inhibitor was studied by using the conventional static system. The mechanism of unimolecular elimination channel is shown below. [...] In this scheme, the total molecular dissociation rate constant, ($k_1\;+\;k_2$), for the decomposition of $BrCH_2CH_2CH_2Cl$ was determined by pyrolyzing the $BrCH_2CH_2CH_2Cl$ in the temperature range of $380-420^{\circ}C$ and in the pressure range of 10∼100 torr. To obtain $k_3\;and\;k_4,\;and\;to\;obtain\;k_1\;and\;k_2$ independently, the thermal decompositions of allyl chloride and allyl bromide were also studied. The Arrhenius parameters for each step are as follows; $log\;A_{\infty}\;=\;14.20(sec^{-1}),\;E_a$ = 56.10(kcal/mol) for reaction path 1; $log\;A_{\infty}\;=\;12.54(sec^{-1}),\;E_a$ = 49.75(kcal/mol) for reaction path 2; $log\;A_{\infty}\;=\;13.41(sec^{-1}),\;E_a$ = 50.04(kcal/mol) for reaction path 3; $log\;A_{\infty}\;=\;12.43(sec^{-1}),\;E_a$ = 52.78(kcal/mol) for reaction path 4; Finally, the experimentally observed pressure dependence of the rate constants in each step is compared with the theoretically predicted values that are obtained by the RRKM calculations.

The polymeric species formed on the hydrolysis of Th(IV) from solubility experiments of $ThO_2$ in 0.1M $NaClO_4$ and $Th(OH)_4\;in\;0.5M\;NaClO_4$ were removed by ultrafiltration using 1 nm ultrafilters. The resultant equilibrium concentrations of mono-hydroxy Th(IV) species in solutions between pH 1.5 to 13 were measured by the NAA method. From these data solubility product of thorium dioxide and the stability constants of mono-hydroxy Th(Ⅳ) were determined. The values obtained were log $K_{sp}\;-\;50.76\;{\pm}\;0.08, log\;{\beta}_{1,1}\;12.42\;{\pm}\;0.02,\;log\;{\beta}_{1,2}\;22.46\;{\pm}\;0.15, log\;{\beta}_{1,3}\;34.36\;{\pm}\;0.07,\;log\;{\beta}_{1,4}\;42.58\;{\pm}\;0.08$, which are in good agreement with the values given in the literature. In addition, several dimeric species, $Th_2(OH)_2\;^{6+},\;Th_2(OH)_3\;^{5+} and\;Th_2(OH)_4\;^{4+}$ have been identified.

The gas-phase reactions of methyl formate with anions, $-NH_2,\;-OH,\;-CH_2CN$, are studied theoretically using the AM1 method. Stationary points are located by the reaction coordinate method, refined by the gradient norm minimization and characterized by the determination of Hessian matrix. Potential energy profiles and the stationary point structures are presented for all conceivable processes. Four reaction paths are found to be possible: formyl proton and methyl proton abstractions, carbonyl addition, and $S_N2$ process. For the most basic anion $-NH_2$ the proton abstraction path is favored, while in other case, $OH\;and\;-CH_2CN$, the carbonyl addition paths are favored. In all cases the $S_N2$ process is the most exothermic, but due to the relatively high activation barrier the process can be ruled out.

Two rhodium(I) complexes of the types [Rh(BPPF)(NBD)]$ClO_4$ (10) and [Rh(BPPF)$Cl]_2$ (11) (BPPF = 1,1'-bis(diphenylphosphino)-ferrocene) have been prepared and investigated as catalysts for the regioselective hydrogenation of polynuclear heteroaromatic nitrogen and sulfur compounds such as quinoline (1), acridine (2), phenanthridine (3), 7,8-benzoquinoline (4), benzothiophene (5), isoquinoline (6), indole (7), pyridine (8), and thiophene (9). Both complexes 10 and 11, except for the cases of indole (7) and mononuclear heteroaromatics 8-9, are very efficient in the selective reduction under quite mild hydrogenation conditions to give the corresponding saturated nitrogen and sulfur heterocyclic analogues of 1-6 in fast conversion rates and in excellent yields. Relative rate studies revealed that the reduction depends significantly on the steric and electronic effects of the substrates. Of the two complexes 10-11, the dimeric species 11 gives faster reaction rates in all cases studied.

Theoretical analysis of DF-$CO_2$ transfer chemical laser is performed through simple kinetic model consisting of 30 chemical reactions. In this model, we calculate the power theoretically by solving the rate equations, which are related to the $D_2\;+\;F_2$ chain reaction and the DF-$CO_2$ resonance energy transfer, combined with both the gain processes and the stimulated emission processes. The calculated powers are verified with previously reported results in good agreements. The output energy rises linearly with the increase in pressure, and the duration time of output pulse show the inverse dependence on pressure. Through the detailed calculation of temperature and concentrations of reactants as a function of time, it is found that the deactivation processes of DF(v) can be neglected in low pressure, but they have to be considered in high pressure. From the parametric study for the variation on [$D_2]/[F_2$] and [$CO_2]/[D_2\;+\;F_2$] at several constant total pressure, the optimum lasing conditions are found to be in a range of 1/3 to 1 and 2 to 4, respectively.

Electronic structures and ethylene addition reaction for halocyclopentynes are investigated using MNDO method. Electronic effects due to the halogen substitution are very small for halocyclopentynes. Fluorocyclopentyne is slightly more stable than cyclopentyne and other halocyclopentynes, but reactivities for cycloaddition reactions are about the same for all halocyclopentynes and cyclopentyne. Stabilization effect is substantial for hexafluorocyclopentyne.

In this work we have experimentally observed the physisorption isotherms for nitrogen, TMS, cyclohexane, benzene, and n-hexane adsorbed on flat aluminum foil surface and have analyzed them theoretically on the basis of the theory proposed by Chang et al. The results show that the theory by Chang et al. can provide a useful means to describe the physisorption of gases on uniform flat solid surface which is essentially important for analysis of the pore volume distribution in porous solid surface. We have also discussed the application of the results obtained in this work to the analysis of pore volume distribution in porous alumina we reported previously.

The strengths of two-photon transitions from the ground state to excited vibronic states in benzene are calculated by using the CNDO/2-U wave functions. The role of vibronic coupling in two-photon absorption process is discussed. The $A_{1{\bar{g}}}-A_{2g}^+$ two-photon transitions, which are forbidden by the identity-forbidden selection rule in single frequency two-photon absorption, are too weak to be experimentally observed even when two photons of different energies are used. It is because the transitions are forbidden also by the pseudo-parity selection rule which are applicable for alternant hydrocarbons such as benzene. It is also shown that the vibronic coupling is not very effective in altering the pseudo-parity property of the electronic state. The strength of the vibronically induced two-photon absorption is strongly affected by the presence of an electronic state from which two-photon absorption can borrow the intensity. It is pointed out that the pseudo-parity selection rule may be violated in such cases.

Species selective spectroelectrochemistry (SSSE) is described by relating the derivative absorbance (dA/dt) signals with electrochemical currents for conventional transient electrochemical experiments. Expressions relating the currents with the dA/dt signals were obtained. From these expressions, physical constants such as coefficients and molar absorptivities of electrogenerated species can be determined. By obtaining both derivative absorbance and current signals concurrently and comparing them, one can perform the SSSE experiments. The utility of the SSSE in sorting out electrochemical information is demonstrated.

The interaction energies of Xenon in n-alkanes were estimated by using three models for the cavity formation process, Hildebrand's regular solution theory, Pierotti's scaled particle theory and Sinanoglu-Reiss-Moura-Ramos' solvophobic theory in an attempt to examine the validity of three models. It appears that Pierotti's implementation of scaled particle theory yields a reasonable estimate of cavity formation energy over a considerable range in solvent size provided that the solute is spherical enough as are the inert gases.