Mechanism of ionic dissociation of HCl in the smallest water clusters.

The dissociation of strong acids into water is a fundamental process in chemistry and biology. Determining the minimum number of water molecules that can result in an ionic dissociation of hydrochloric acid (HCl → H+ + Cl-) remains a challenging subject. In this study, the reactions of H2O with HCl(H2O)n-1 (HCl-H2O cluster), i.e., HCl(H2O)n-1 + H2O (n = 3-7), were investigated by using the direct ab initio molecular dynamics (AIMD) method. Direct AIMD calculations were performed to set the collision energy of H2O to zero for all trajectories. For n = 3, no reaction occurred. In contrast, HCl dissociated to H+ + Cl- at n = 4, forming a contact ion pair (cIP) and solvent-separated ion pair (ssIP) as products. The reactions were expressed as HCl(H2O)3 + H2O → H3O+(H2O)2Cl- (ssIP), and HCl(H2O)3 + H2O → H3O+(Cl-)(H2O)2 (cIP). The ion pair (IP) products were dependent on the collision site of H2O relative to HCl(H2O)3. For n = 5-7, both IPs were formed through the reaction between H2O and HCl(H2O)n-1 (n = 5-7). The reaction between HCl and (H2O)4 (HCl + (H2O)4 → HCl(H2O)4) was non-reactive in IP formation. The reaction mechanism was discussed based on the theoretical results.

Aluminum-Doping Effects on the Electronic States of Graphene Nanoflake: Diffusion and Hydrogen Storage Mechanism.

Graphene nanoflakes are widely utilized as high-performance molecular devices due to their chemical stability and light weight. In the present study, the interaction of aluminum species with graphene nanoflake (denoted as GR-Al) has been investigated using the density functional theory (DFT) method to elucidate the doping effects of Al metal on the electronic states of GR. The mechanisms of the diffusion of Al on GR surface and the hydrogen storage of GR-Al were also investigated in detail. The neutral, mono-, di-, and trivalent Al ions (expressed as Al, Al+, Al2+, and Al3+, respectively) were examined as the Al species. The DFT calculations showed that the charge transfer interaction between Al and GR plays an important role in the binding of Al species to GR. The diffusion path of Al on GR surface was determined: the barrier heights of Al diffusion were calculated to be 2.1-2.8 kcal mol-1, which are lower than Li+ on GR (7.2 kcal/mol). The possibility of using GR-Al for hydrogen storage was also discussed on the basis of the theoretical results.

C-C Bond Formation Reaction Catalyzed by a Lithium Atom: Benzene-to-Biphenyl Coupling.

Transition-metal-catalyzed carbon-carbon (C-C) bond formation is an important reaction in pharmaceutical and organic chemistry. However, the reaction process is composed of multiple steps and is expensive owing to the presence of transition metals. This study proposes a lithium-catalyzed C-C coupling reaction of two benzene molecules (Bz) to form a biphenyl molecule, which is a transition-metal-free reaction, based on ab initio and direct ab initio molecular dynamics (AIMD) calculations. The static ab initio calculations indicate that the reaction of two Bz molecules with Li- ions (reactant state, RC) can form a stable sandwiched complex (precomplex), where the Li- ion is sandwiched by two Bz molecules. The complex formation reaction can be expressed as 2Bz + Li - → Bz(Li -)Bz, where the C-C distance between the Bz rings is 2.449 Å. This complex moves to the transition state (TS) via the structural deformation of Bz(Li-)Bz, where the C-C distance is shortened to 2.118 Å. The barrier height was calculated to be -9.9 kcal/mol (relative to RC) at the MP2/6-311++G(d,p) level. After TS, the C(sp3)-C(sp3) single bond was completely formed between the Bz rings (the C-C bond distance was 1.635 Å) (late complex). After the dissociation of H2 from the late complex, a biphenyl molecule was formed: the C(sp2)-C(sp2) bond. The calculations suggest that the C-C bond coupling of Bz occurred spontaneously from 2Bz + Li-, and biphenyl molecules were directly formed without an activation barrier. Direct AIMD calculations show that the C-C coupling reaction also takes place under electron attachment to Li(Bz)2: Li(Bz)2 + e- → [Li-(Bz)2]ver → precomplex → TS → late complex, where [Li-(Bz)2]ver is the vertical electron capture species of Li(Bz)2. Namely, the C-C coupling reaction spontaneously occurred in Li(Bz)2 owing to electron attachment. Similar C-C coupling reactions were also observed for halogen-substituted benzene molecules (Bz-X, X = F and Cl). Furthermore, this study discusses the mechanism of C-C bond formation in electron capture based on the theoretical results.

Formation Mechanism of Odd- and Even-Numbered Hydrogen Cluster Cations Using the Direct Ab Initio Molecular Dynamics Approach.

The photoreaction of hydrogen clusters caused by cosmic-ray irradiations plays a crucial role in interstellar molecular clouds because the reaction of molecules takes place in these surrounding clusters. Previous gas-phase experiments introduced the reaction products after the ionization of the neutral hydrogen cluster. In the experiments, the odd-numbered hydrogen cluster cation, H+(H2)m, was the main product, while the even-numbered cluster cation, (H2)n+, was the minor product. However, the formation yield of (H2)n+ was significantly low. Despite many theoretical calculations and experiments, the formation mechanism of odd- and even-numbered cluster ions from ionized hydrogen clusters is still unclear. In this study, the direct ab initio molecular dynamics (AIMD) method was applied to the reaction of the hydrogen cluster cation (H2)n+ to understand the abovementioned formation mechanism. The trajectories of (H2)n+ following the vertical ionization of the neutral cluster were calculated. Direct AIMD calculations indicated that odd-numbered cluster cations, H3+(H2)n-2 + H (dissociation), were formed directly as the main product after the ionization of (H2)n. An even-numbered cluster, (H2)n+, was temporally formed when an H-shaped complex composed of three H2 molecules existed within a neutral cluster. However, it was rapidly dissociated to an odd-numbered cluster. Static ab initio calculations suggested that the odd-numbered cluster complex, H3+(H2)n-2-H, could be transferred to even-numbered ions via a transition state with a low energy barrier. The even-numbered cluster cation was formed stepwise from the odd-numbered cluster cation. The formation mechanism of odd- and even-numbered cluster cations is discussed based on these results.

Intracluster Reaction Dynamics of Ionized Micro-Hydrated Hydrogen Peroxide (H2O2): A Direct Ab Initio Molecular Dynamics Study.

Hydrogen peroxide (H2O2) is a unique molecule that is applied in various fields, including energy chemistry, astrophysics, and medicine. H2O2 readily forms clusters with water molecules. In the present study, the reactions of ionized H2O2-water clusters, H2O2 +(H2O) n , after vertical ionization of the parent neutral cluster were investigated using the direct ab initio molecular dynamics (AIMD) method to elucidate the reaction mechanism. Clusters with one to five water molecules, H2O2-(H2O) n (n = 1-5), were examined, and the reaction of [H2O2 +(H2O) n ]ver was tracked from the vertical ionization point to the product state, where [H2O2 +(H2O) n ]ver is the vertical ionization state (hole is localized on H2O2). After ionization, fast proton transfer (PT) from H2O2 + to the water cluster (H2O) n was observed in all clusters. The HOO radical and H3O+(H2O) n-1 were formed as products. The PT reaction proceeds directly without an activation barrier. The PT times for n = 1-5 were calculated to be 36.0, 9.8, 8.3, 7.7, and 7.1 fs, respectively, at the MP2/6-311++G(d,p) level, indicating that PT in these clusters is a very fast process, and the PT time is not dependent on the cluster size (n), except in the case of n = 1, where the PT time was slightly longer because the bond distance and angle of the hydrogen bond in n = 1 were deformed from the standard structure. The reaction mechanism was discussed based on these results.

Structures and electronic states of trimer radical cations of coronene: DFT-ESR simulation study.

Coronene (C24H12), a charge transfer complex with low-cost and high-performance energy storage, has recently attracted attention as a model molecule of graphene nano-flakes (GNFs). The stacking structures of the trimer radical cation correlate strongly with the conduction states of the GNFs. In the present paper, the structures and electronic states of the monomer, dimer and trimer radical cations of coronene were investigated by means of density functional theory calculations. In particular, the proton hyperfine coupling constants of these species were determined. The radical cation of coronene+ (monomer) showed two structures corresponding to the 2Au and 2B3u states due to the Jahn-Teller effect. The 2Au state was more stable than the 2B3u state, although the energy difference between the two states was only 0.03 kcal mol-1. The dimer and trimer radical cations took stacking structures distorted from a full overlap structure. The intermolecular distances of the molecular planes were 3.602 Å (dimer) and 3.564 and 3.600 Å (trimer). The binding energies of the dimer and trimer were calculated to be 8.7 and 13.3 kcal mol-1, respectively. The spin density was equivalently distributed on both coronene planes in the dimer cation. In contrast, the central plane in the trimer cation had a larger spin density, ρ = 0.72, than the upper and lower planes, both with ρ = 0.14. The proton hyperfine coupling constants calculated from these structures and the electronic states of the monomer, dimer, and trimer radical cations of coronene were in excellent agreement with previous ESR spectra of coronene radical cations. The structures and electronic states of (coronene)n+ (n = 1-3) were discussed on the basis of the theoretical results.

Reaction mechanism of an intracluster SN2 reaction induced by electron capture.

Bimolecular nucleophilic substitution (SN2) reactions have been widely investigated from both experimental and theoretical points of view because they represent one of the simplest organic reactions. Most studies on SN2 reactions have been focused on bimolecular collision. In contrast, information on intracluster SN2 reactions is limited. In this study, an intracluster SN2 reaction of NF3-CH3Cl triggered by electron attachment was investigated using a direct ab initio molecular dynamics (AIMD) method. In the structure of NF3-CH3Cl, the N-F bond in NF3 is oriented collinearly toward the carbon atom of CH3Cl. After electron capture by NF3-CH3Cl, the F- ion that is generated from the (NF3)- moiety collides with the carbon atom of CH3Cl. The intracluster SN2 reaction occurs as follows: (NF3-CH3Cl)- (electron capture state) → NF2-(F-)-CH3Cl (pre-reaction complex) → transition state (TS) → NF2-CH3F-Cl- (post-reaction complex) → NF2 + CH3F + Cl- (product state). The reaction energy is efficiently transferred to the translational mode of Cl-, and the Cl- ion with a high translational energy is then removed from the system. This energy is significantly larger than that of Cl- formed in the bimolecular SN2 reaction (F- + CH3Cl). The reaction mechanism is discussed based on the theoretical results.

Reaction Dynamics of NO+ with Water Clusters.

The reaction of NO+ with water molecules plays a crucial role in the D-region of the atmosphere because the reaction provides nitrous acid (HONO) and protonated water species (H3O+). In this study, the reaction of NO+ with water clusters, NO+ + (H2O)n (n = 1-7), was investigated by means of the direct ab initio molecular dynamics method to elucidate the reaction mechanism of NO+ in the atmosphere from a theoretical viewpoint. At n = 1 and 2, the reaction of NO+ with (H2O)n led to the formation of a complex: NO+ + (H2O)n → NO+(H2O)n (n = 1 and 2). At n = 3, the formation channel of HONO was open, and HONO was formed according to NO+ + (H2O)n → HONO---H+(H2O)n-1 (n = 3), through which H3O+ was also formed as H+(H2O)2. However, the HONO formation efficiency was significantly low for n = 3. In large clusters with n = 4-7, the HONO formation channel became the main channel, and the dissociation of HONO from the HONO--H+(H2O)n-1 complex occurred in part: NO+ + (H2O)n → HONO---H+(H2O)n-1 → HONO + H+(H2O)n-1. The energetics and reaction mechanism were discussed on the basis of theoretical results.

Theoretical study of the dissociative photodetachment dynamics of the hydrated superoxide anion cluster.

The dissociative photodetachment of the hydrated superoxide anion cluster, O2-·H2O + hν → O2 + H2O + e-, is theoretically investigated using path-integral and ring-polymer molecular dynamics simulation methods, which can account for nuclear quantum effects. Full-dimensional potential energy surfaces for the anionic and lowest two neutral states (triplet and singlet spin states) are constructed based on extensive density-functional theory calculations. The calculated photoelectron spectrum agrees well with the experimental spectra measured for different photodetachment laser wavelengths. The calculated photoelectron-photofragment kinetic energy correlation spectrum also agrees well with previous experimental measurements. The dissociation mechanisms, including available energy partitioning and the importance of nuclear quantum effects in photodetachment, are discussed in detail.

Reactions of Photoionization-Induced CO-H2O Cluster: Direct Ab Initio Molecular Dynamics Study.

The hydrocarboxyl radical (HOCO) is an important species in combustion and astrochemistry because it is easily converted to CO2 after hydrogen reduction. In this study, the formation mechanism of the HOCO radical in a CO-H2O system was investigated by direct ab initio molecular dynamics calculations. Two reactions were examined for HOCO formation. First, the reaction dynamics of the CO-H2O cluster cation, following the ionization of the neutral parent cluster CO(H2O) n (n = 1-4), were investigated. Second, the bimolecular collision reaction between CO and (H2O) n + was studied. In the ionization of the CO(H2O) n clusters (n = 3 and 4), proton transfer, expressed as CO(H2O) n + → CO-(OH)H3O+(H2O) n -2, occurred within the (H2O) n + cluster cation, and the HOCO radical was yielded as a product upon addition of CO and OH. This reaction proceeds under zero-point energy. Also, this radical was effectively formed from the collision reaction of CO with water cluster cation (H2O) n +, expressed as CO + OH(H3O+)(H2O) n -2 → HOCO-H3O+ + (H2O) n -2. If the intermolecular vibrational stretching mode is excited in the CO(H2O) n cluster (vibrational stretching between CO and the water cluster), the HOCO radical was detected after ionization when n = 2. The reaction mechanism was discussed based on the theoretical results.

Formation of Hydrogen Peroxide from O-(H2O)n Clusters.

Hydrogen peroxide (H2O2) has recently received much attention as a safe and clean energy carrier for hydrogen molecules. In this study, based on direct ab initio molecular dynamics (AIMD) calculations, we demonstrated that H2O2 is directly formed via the photoelectron detachment of O-(H2O)n (n = 1-6) (water clusters of an oxygen radical anion). Three electronic states of oxygen atoms were examined in the calculations: O(X)(H2O)n (X = 3P, 1D, and 1S states). After the photoelectron detachment of O-(H2O)n (n = 1) to the 1S state, a complex comprising O(1S) and H2O, O(1S)-OH2, was formed. A hydrogen atom of H2O immediately transferred to O(1S) during an intracluster reaction to form H2O2 as the final product. Simulations were run to obtain a total of 33 trajectories for n = 1 that all led to the formation of H2O2. The average reaction time of H2O2 formation was calculated to be 57.7 fs in the case of n = 1, indicating that the reaction was completed within 100 fs of electron detachment. All the reaction systems O(1S)(H2O)n (n = 1-6) indicated the formation of H2O2 by the same mechanism. The reaction times for n = 2-6 were calculated to range between 80 and 180 fs, indicating that the reaction for n = 1 is faster than that of the larger clusters, that is, the larger the cluster size, the slower the reaction is. The reaction dynamics of the triplet O(3P) and singlet O(1D) potential energy surfaces were calculated for comparison. All calculations yielded the dissociation product O(X)(H2O)n → O(X) + (H2O)n (X = 3P and 1D), indicating that the O(1S) state contributes to the formation of H2O2. The reaction mechanism was discussed based on the theoretical results.

Molecular Design of a Reversible Hydrogen Storage Device Composed of the Graphene Nanoflake-Magnesium-H2 System.

Carbon materials such as graphene nanoflakes (GRs), carbon nanotubes, and fullerene can be widely used for hydrogen storage. In general, metal doping of these materials leads to an increase in their H2 storage density. In the present study, the binding energies of H2 to Mg species on GRs, GR-Mg m+ (m = 0-2), were calculated using density functional theory calculations. Mg has a wide range of atomic charges. In the case of GR-Mg (m = 0, Mg atom), the binding energy of one H2 molecule is close to 0, whereas those for m = 1 (Mg+) and 2 (Mg2+) are 0.23 and 13.2 kcal/mol (n = 1), respectively. These features suggest that GR-Mg2+ has a strong binding affinity toward H2, whereas GR-Mg+ has a weak binding energy. In addition, it was found that the first coordination shell is saturated by four H2 molecules, GR-Mg2+-(H2) n (n = 4). Next, direct ab initio molecular dynamics calculations were carried out for the electron-capture process of GR-Mg2+-(H2) n and a hole-capture process of GR-Mg+-(H2) n (n = 4). After electron capture, the H2 molecules left and dissociated from GR-Mg+: GR-Mg2+-(H2) n + e- → GR-Mg+ + (H2) n (H2 is released into the gas phase). In contrast, the H2 molecules were bound again to GR-Mg2+ after the hole capture of GR-Mg+: GR-Mg+ + (H2) n (gas phase) + hole → GR-Mg2+-(H2) n . On the basis of these calculations, a model device with reversible H2 adsorption-desorption properties was designed. These results strongly suggest that the GR-Mg system is capable of H2 adsorption-desorption reversible storage.

Proton Transfer Reaction Rates in Phenol-Ammonia Cluster Cation.

Proton transfer (PT) in an interaction system of a hydroxyl-amino group (OH-NH) plays a crucial role in photoinduced DNA and enzyme damage. A phenol-ammonia cluster is a prototype of an OH-NH interaction and is sometimes used as a DNA model. In the present study, the reaction dynamics of phenol-ammonia cluster cations, [PhOH-(NH3)n]+ (n = 1-5), following ionization of the neutral parent clusters, were investigated using a direct ab initio molecular dynamics (AIMD) method. In all clusters, PTs from PhOH+ to (NH3)n were found postionization, the reaction of which is expressed as PhOH+-(NH3)n → PhO-H+(NH3)n. The time of the PT was calculated as 43 (n = 1), 26 (n = 2), and 13 fs (n = 3-5), suggesting that the rate of PT increases with an increase in n and is saturated at n = 3-5. The difference in the PT rate originates strongly from the proton affinity of the (NH3)n cluster. In the case of n = 3-5, a second PT was found, the reaction of which is expressed as PhO-H+(NH3)n → PhO-NH3-H+(NH3)n-1, and a third PT occurred at n = 4 and 5. The time of the PT was calculated as 10-13 (first PT), 80-100 (second PT), and 150-200 fs (third PT) in the case of larger clusters (n = 4 and 5). The reaction mechanism based on the theoretical results is discussed herein.

Hydrogen Dissociation Dynamics from Water Clusters on Triplet-State Energy Surfaces.

The ice surface provides two-dimensional reaction fields for bimolecular collisions in interstellar space. As H2O molecules on the surface are typically exposed to cosmic rays, H2O in the excited state is easily dissociated into H + OH, where a H atom is released from the surface to the gas phase. In the present study, the reaction dynamics of small-sized water clusters on the triplet-state potential energy (T1) surface, following the vertical electronic excitation from the ground state (S0), were investigated using direct ab initio molecular dynamics to provide insights into the generation mechanism of H atoms from an irradiated ice surface. In all clusters, that is, (H2O)n (n = 2-6), the H atom was directly dissociated from one of the H2O molecules in the clusters (direct dissociation), whereas the OH radical remained in the cluster. In the branched form of H2O tetramer (n = 4) and the book form of H2O hexamer (n = 6), the dissociated hydrogen atom (H') collided with the neighboring H2O molecule, and the exchange of H atoms occurred as H' + H2O → H'-H2O (collision) → H'OH + H (hydrogen exchange). The translational energy of the exchanged H atom decreases significantly (by approximately 50%) because the kinetic energy of the H' atom is efficiently transferred to the vibrational modes of the cluster during the H-exchange reaction. The mechanism of H atom dissociation is discussed based on theoretical results.

Proton Transfer vs Complex Formation Channels in Ionized Formic Acid Dimer: A Direct Ab Initio Molecular Dynamics Study.

Photoirradiation to a hydrogen-bonded system plays an important role in the initial DNA and enzyme damage processes. The formic acid (FA) dimer is a model compound of double proton transfer systems, such as DNA base pairs. In the present study, the reactions of the FA dimer cation, formed upon ionization of the neutral dimer, have been investigated by the direct ab initio molecular dynamics method. Two reaction channels were identified for the FA dimer cation: complex formation and proton transfer (PT). In the complex formation channel, the carbonyl oxygen atoms of the two FA monomers were bound symmetrically, and a face-to-face complex was formed. In the PT channel, the proton of FA+ was transferred to FA, forming the H+(HCOOH)--HCO2 radical cation as product. At low temperature, the complex channel was dominant, whereas the PT channel increased with increasing temperature. The asymmetric spin distribution on the FA dimer cation exhibited a strong correlation with the PT channel.

Intramolecular Reactions in Ionized Ammonia Clusters: A Direct Ab Initio Molecular Dynamics Study.

Ammonia cluster cations are a chemical species that has recently attracted considerable research attention as an ion-molecule reaction species in the planetary atmosphere, surface reaction species in materials chemistry, and super-alkali species. Reactions of the radical cation of an ammonia cluster, [(NH3)n]+ (n = 2-6), following the ionization of the parent neutral cluster, were investigated using direct ab initio molecular dynamics to elucidate the reactions of the ammonia cluster cation under astrochemical conditions. The calculations showed that two competing reaction channels-proton transfer (PT) channel and complex formation channel-operate after the ionization of neutral clusters. In the PT channel, a proton of NH3+ was transferred to a neighboring ammonia molecule. The PT channel was found in all clusters (n = 2-6). Reaction via the PT channel became faster with increasing cluster size and saturated around n = 5-6. In the complex formation channel, a face-to-face complex having a H3N-NH3+ structure (with a N-N bond) was formed. This channel was found only in larger clusters (n = 5-6). Time scales of PT and complex formation channels were calculated to be 20-30 and 40-50 fs, respectively. The reaction mechanism was discussed based on the results of theoretical calculations.

Activation of CO2 in Photoirradiated CO2-H2O Clusters: Direct Ab Initio Molecular Dynamics (MD) Study.

Carbon dioxide (CO2) is one of the stable and inactive molecules that contribute to greenhouse gases. The development of new reactions of CO2 activation, chemical fixation, and conversion is a very important issue. In this report, the reactions of CO2-H2O binary clusters were investigated using a direct ab initio molecular dynamics (AIMD) method to find a new reaction of CO2 activation. Clusters composed of carbon dioxide and water molecules, CO2(H2O) n ( n = 2-5), were utilized as a model of the binary cluster. The reaction dynamics of [CO2(H2O) n]+ following the ionization of parent neutral clusters were also investigated. Two electronic states of [CO2(H2O) n]+ were examined for direct AIMD surfaces: CO2[(H2O) n]+ (ground state) and (CO2)+(H2O) n (excited charge transfer (CT) state). After the ionization of the clusters, a proton-transfer (PT) reaction occurred within the (H2O) n+ moiety at the ground state, whereas the reactive HCO3 radical was formed at the CT state for OH addition to CO2+: CO2+(H2O) n → HCO3 + H+(H2O) n-1. The mechanisms of the PT process and the HCO3 radical formation were discussed based on the theoretical results.

Water-accelerated π-Stacking Reaction in Benzene Cluster Cation.

Single molecule electron devices (SMEDs) have been widely studied through both experiments and theoretical calculations because they exhibit certain specific properties that general macromolecules do not possess. In actual SMED systems, a residual water molecule strongly affects the electronic properties of the SMED, even if only one water molecule is present. However, information about the effect of H2O molecules on the electronic properties of SMEDs is quite limited. In the present study, the effect of H2O on the ON-OFF switching property of benzene-based molecular devices was investigated by means of a direct ab initio molecular dynamics (AIMD) method. T- and H-shaped benzene dimers and trimers were examined as molecular devices. The present calculations showed that a H2O molecule accelerates the π-stacking formation in benzene molecular electronic systems. The times of stacking formation in a benzene dimer cation (n = 2) were calculated to be 460 fs (H2O) and 947 fs (no-H2O), while those in a trimer cation (n = 3) were 551 fs (H2O) and 1019 fs (no-H2O) as an average of the reaction time. This tendency was not dependent on the levels of theory used. Thus, H2O produced positive effects in benzene-based molecular electronics. The mechanism of π-stacking was discussed based on the theoretical results.

Jahn-Teller Effect of the Benzene Radical Cation: A Direct ab Initio Molecular Dynamics Study.

The benzene radical cation (Bz+) is a typical model molecule of the Jahn-Teller (J-T) active species. Bz+ has two structural forms due to the J-T effect. These are the compressed and elongated forms, expressed as Bz+(comp) and Bz+(elong), respectively. In Bz+(comp), the hexagonal structure of the benzene ring is compressed up and down, and in Bz+(elong), it is pulled up and down. From electron spin resonance experiments, it was found that Bz+ takes a compressed form in low-temperature Freon matrices (CF3Cl and CF2ClCFCl2), whereas the elongated form was found in argon matrices. However, the selectivity of these structural forms is still unclear. In this study, the ionization dynamics of isolated benzene (Bz) and benzene-M complexes (where M denotes counter-molecules, M = NH3, H2O, CF3Cl, CH4, CH3OH, Ar, SH2, ammonia dimer, or water dimer) have been investigated by means of the direct ab initio molecular dynamics (AIMD) method in order to shed light on the Bz+ formation mechanism. The static ab initio calculations showed that Bz+(comp) is slightly more energetically stable than Bz+(elong), although the energy difference was only 0.1 kcal/mol at the CCSD/6-311++G(d,p) level. The direct AIMD calculations indicated that Bz+(comp) was formed from the Bz-M complexes when M was NH3, CF3Cl, or an ammonia dimer, whereas the ionization of Bz-M when M was H2O, CH4, CH3OH, SH2, or a water dimer formed Bz+(elong). In the case of complexes with an argon dimer, Bz(Ar)2, both forms were obtained from a slight orientation change of Ar on Bz. A selective rule is discussed on the basis of the calculated results.

Proton Transfer Rates in Ionized Hydrogen Chloride-Water Clusters: A Direct Ab Initio Molecular Dynamics Study.

Reactions of the microhydrated hydrogen chloride radical cation, [HCl-(H2O)n]+ (n = 1-5), following the ionization of the parent neutral cluster were investigated by the direct ab initio molecular dynamics (AIMD) method to elucidate the cluster size dependence of the proton transfer (PT) rate in the ionized state. The ionization occurred from the HCl moiety of the clusters. The proton of HCl+ was transferred to the neighboring water molecule in the cluster. The time of PT was strongly dependent on the cluster size (n); the time of PT decreased with increasing n and reached a limiting value at n = 4-5 (the time of PT was ca. 7 fs). The acceleration of the PT rate was mainly caused by the shortness of the hydrogen bond between HCl+ and H2O in larger clusters, that is, a short hydrogen bond causes fast PT. The electrostatic effects of the water cluster further accelerated the rate of PT. After the first PT from HCl+ to H2O, the second PT (H3O+ + H2O →H2O + H3O+) was detected for n = 3-5. The times of the first and second PTs were calculated as 7-15 and 30-40 fs, respectively. The reaction mechanism was discussed based on the theoretical results.