The ionization dynamics of the water clusters (H 2 O) n (n ) 3-6) have been investigated by means of the full-dimensional direct ab initio trajectory method. The static ab initio and DFT calculations were carried out at the HF/6-311G(d,p) and B3LYP/6-311G(d,p) levels, whereas the direct ab initio trajectory calculations were performed at the HF/6-31G(d) and 6-311G(d,p) levels of theory. The static ab initio and DFT calculations showed that the most stable structure is the cyclic form for all cases (n ) 3-6). In the ionization of the water trimer, the complex (H 3 O + OH)H 2 O was obtained as a product (complex formation channel). In the larger clusters (n ) 4-6), the OH dissociation was only found after the ionization of (H 2 O) n (OH dissociation channel). The OH dissociation occurs via two-step processes: the first step is a proton-transfer process from H 2 O + to H 2 O along the hydrogen bond in the cluster, and then the (H 3 O + OH) complex is formed as a core in the cluster, expressed by (The next step is the second protontransfer process from H 3 O + OH to the neighboring water molecule, which is expressed by (OH)-H 3 O + -H 2 O f (OH)-H 2 O-H 3 O + . It was found that the OH dissociation takes place immediately after the second proton transfer. The lifetimes of the intermediate complexes are distributed in the range 50-200 fs for n ) 4-6. The reaction mechanism was discussed on the basis of theoretical results.

Diffusion processes of the Li+ ion on a model surface of amorphous carbon (Li+C96H24 system) have been investigated by means of the direct molecular orbital (MO) dynamics method at the semiempirical AM1 level. The total energy and energy gradient on the full-dimensional AM1 potential energy surface were calculated at each time step in the dynamics calculation. The optimized structure, where Li+ is located in the center of the cluster, was used as the initial structure at time zero. The dynamics calculation was carried out in the temperature range 100-1000 K. The calculations showed that the Li+ ion vibrates around the equilibrium point below 200 K, while the Li+ ion moves on the surface above 250 K. At intermediate temperatures (300 K < T < 400 K), the ion moves on the surface and falls in the edge regions of the cluster. At higher temperatures (600 K < T), the Li+ ion transfers freely on the surface and edge regions. The diffusion pathway of the Li+ ion was discussed on the basis of theoretical results.

Direct molecular orbital-molecular dynamics (MO-MD) calculation was applied to diffusion processes of the Li atom on a model surface of amorphous carbon and compared with the diffusion mechanism of Li+ ion. A carbon sheet composed of C96H24 was used as the model surface. The total energy and energy gradient on the full dimensional potential energy surface of the LiC96H24 system were calculated at each time step in the trajectory calculation. The optimized structure, where the Li atom is located at the center of mass of the model surface, was used as the initial structure at time zero. Simulation temperatures were chosen in the range of 200-1250 K. The dynamics calculations showed that the Li atom vibrates around the initial position below 250 K, and it moves above 300 K. At middle temperature, the Li atom translates freely on the surface. At higher temperature (1000 K), the Li atom moves from the center to edge region of the model surface and is trapped in the edge. The activation energy calculated for the Li atom is larger than that for the Li+ ion. This difference is due to the fact that the Li atom diffuses together with an unpaired electron on the carbon surface. The diffusion mechanism of the Li atom was discussed on the basis of the theoretical results.

Ionization processes of benzene-water cluster Bz(H 2 O) n (n ) 1 and 2) have been studied by means of direct ab initio dynamics calculations. The ab initio calculations for the BzH 2 O 1:1 neutral complex show that in the minimum energy structure the water hydrogens point toward the center of mass of the benzene ring (the dipole orientation form). The potential energy curve calculated as a function of the benzene-H 2 O center of mass distance (R cm ) indicates that the H 2 O molecule is weakly bound to the benzene ring. The potential energy curve for the cationic system BzH 2 O + constrained to the dipole orientation form is purely repulsive, whereas the curve calculated for the oxygen orientation form has a fairly deep well. The complex has a wide Franck-Condon (FC) region for the ionization. Dynamics of the ionization process of the BzH 2 O complex was studied by means of direct ab initio dynamics calculations. A total of 11 points in the FC region were chosen as initial points. The trajectories started from both the equilibrium point of BzH 2 O (R cm ) 3.395 Å) and the outer classical turning point in the FC region (R cm ) 3.60 Å) gave a strongly bound BzH 2 O + complex as a product, whereas the trajectory from the inner classical turning point (R cm ) 2.95 Å) leads to the dissociation product (Bz + + H 2 O). The reaction mechanism of the ionization processes of the BzH 2 O complex was discussed on the basis of these theoretical results.

Cross-coupling between bromoarenes and [(E)-CH3CH=CHCH2BF3]K (2a) by a catalyst prepared from Pd(OAc)2 and D-t-BPF selectively provided γ-coupling products via SE2′ substitution. Mechanistic study of transmetalation revealed a heretofore unknown process, namely, formation of a highly electrophilic [Pd(Ar)(D-t-BPF)]+ before transmetalation with 2a. Thus, kinetic data in coupling of 4-substituted bromoarenes with 2a showed a linear positive correlation (ρ = −1.1) accelerated by donating substituents. This rate-determining role of transmetalation was further confirmed by kinetic data between oxidative adducts [Pd(Ar)(Br)(D-t-BPF)] and 2a that exhibited an analogous correlation with a negative ρ-value (−0.50). Theoretical study by density functional theory (DFT) calculation showed that transmetalation between [Ar−Pd]+ and 2a via an SE2′ (open) transition state is a slightly lower energy process than an SE2′ (closed) process. Allylic substitutions with chiral catalysts are the current topics for enantioselective C−C bond formation, but the catalysts that are effective for allylic nucleophiles have remained unexplored. Among the ligands screened, (R,S)-CyPF-t-Bu was found to achieve 77−90% ee for representative para- and meta-substituted bromoarenes and 2-bromo-1-alkenes in refluxing aqueous tetrahydrofuran (THF) or MeOH. To obtain mechanistic information on enantioselection, the mode of substrate coordination to a cationic phenylpalladium intermediate was calculated, that is, the reaction stage directly preceding the stereodetermining insertion step by DFT calculation. A stable adduct between [Pd(CyPF-t-Bu)(Ph)]+ and 2a located at the C−C double bond from its re-face yielding the experimentally observed R-product is preferred thermodynamically rather than the corresponding si-coordination.