• Bulletin of the Korean Chemical Society
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• 제27권12호
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• pp.1976-1980
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• 2006

We have calculated the reaction probability and the reaction cross-section of the $N(^4S)+O_2(X^3\sum_{g}^{-})\;\rightarrow\;NO(X^2\Pi)+O(^3P)$ reaction by the quasiclassical trajectory method with the 6th-order explicit symplectic algorithm, based on a new ground potential energy surface. The advantage of the 6th-order explicit symplectic algorithm, conserving both the total energy and the total angular momentum of the reaction system during the numerical integration of canonical equations, has firstly analyzed in this work, which make the calculation of the reaction probability more reliable. The variation of the reaction probability with the impact parameter and the influence of the relative translational energy on the reaction cross-section of the reaction have been discussed in detail. And the fact is found by the comparison that the reaction probability and the reaction cross-section of the reaction estimated in this work are more reasonable than the theoretical ones determined by Gilibert et al.

• Bulletin of the Korean Chemical Society
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• 제32권5호
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• pp.1527-1533
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• 2011

The reaction of gas-phase atomic hydrogen with oxygen atoms chemisorbed on a silicon surface is studied by use of the classical trajectory approach. We have calculated the probability of the OH formation and energy deposit of the reaction exothermicity in the newly formed OH in the gas-surface reaction H(g) + O(ad)/Si${\rightarrow}$ OH(g) + Si. All reactive events occur in a single impact collision on a subpicosecond scale, following the Eley-Rideal mechanism. These events occur in a localized region around the adatom site on the surface. The reaction probability is dependent upon the gas temperature and shows the maximum near 1000 K, but it is essentially independent of the surface temperature. The reaction probability is also independent upon the initial excitation of the O-Si vibration. The reaction energy available for the product state is carried away by the desorbing OH in its translational and vibrational motions. When the initial excitation of the O-Si vibration increases, translational and vibrational energies of OH rise accordingly, while the energy shared by rotational motion varies only slightly. Flow of energy between the reaction zone and the solid has been incorporated in trajectory calculations, but the amount of energy propagated into the solid is only a few percent of the available energy released in the OH formation.

• Bulletin of the Korean Chemical Society
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• 제12권6호
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• pp.652-658
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• 1991

The effect of intermolecular collisions in the infrared multiphoton dissociation (IRMPD) of difluorochloromethane was investigated using He, Ar, and $N_2$ as buffer gases. The reaction probability for IRMPD of difluorochloromethane was measured as a function of laser fluence and the buffer gas pressure under unfocused beam geometry. It was observed that the reaction probability was initially enhanced with the increase of buffer gas pressure up to about 20 torr, but showed a decline at higher pressures. The reaction probability increases monotonically with the laser fluence, but the rate of increase diminishes at higher fluences. An attempt was made to simulate the experimental results by the method of energy grained master equation (EGME). From the parameters that fit the experimental data, the average energy loss per collision, $<{\Delta}E>_d$, was estimated for the He, Ar, and $N_2$ buffer gases.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.151-157
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• 2014

We have reported the reaction probability, integral reaction cross section, and rate constant for the title system calculated with the aid of a time-dependent wave packet approach. The ab initio potential energy surface (PES) of Prudente et al. (Chem. Phys. Lett. 2009, 474, 18) is employed for the purpose. The calculations are carried out over the collision energy range of 0.05-1.4 eV for the two reaction channels of H + LiH ${\rightarrow}$ Li + $H_2$ and $H_b$ + $LiH_a$ ${\rightarrow}$ $LiH_b$ + $H_a$. The Coriolis coupling (CC) effect are taken into account. The importance of including the Coriolis coupling quantum scattering calculations are revealed by the comparison between the Coriolis coupling and the centrifugal sudden (CS) approximation calculations.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1136-1144
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• 1999

The collision-induced reaction of gas-phase atomic hydrogen with hydrogen atoms chemisorbed on a silicon (001)-(2×1) surface is studied by use of the classical trajectory approach. The model is based on reaction zone atoms interacting with a finite number of primary system silicon atoms, which then are coupled to the heat bath, i.e., the bulk solid phase. The potential energy of the Hads‥Hgas interaction is the primary driver of the reaction, and in all reactive collisions, there is an efficient flow of energy from this interaction to the Hads-Si bond. All reactive events occur on a subpicosecond scale, following the Eley-Rideal mechanism. These events occur in a localized region around the adatom site on the surface. The reaction probability shows the maximum near 700K as the gas temperature increases, but it is nearly independent of the surface temperature up to 700 K. Over the surface temperature range of 0-700 K and gas temperature range of 300 to 2500 K, the reaction probability lies at about 0.1. The reaction energy available for the product states is small, and most of this energy is carried away by the desorbing H2 in its translational and vibrational motions. The Langevin equation is used to consider energy exchange between the reaction zone and the bulk solid phase.

• Journal of Photoscience
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• 제12권2호
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• pp.101-107
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• 2005

Infrared multiphoton dissociation of $CHCl_2F$ was studied using $CO_2$ laser excitation. Three products, $C_2Cl_2F_2$, $C_2ClF_3$, and $C_2HClF_2$, were identified by the analysis of the gas mixture from the photoreaction of $CHCl_2F$. The dependence of the reaction probability on added Ar gas pressure and excitation laser pulse energy was investigated. At low pressure (< 10 torr), the reaction probability increased as Ar pressure increased due to the rotational hole-filling effect, while it diminished with the increase of Ar pressure at high pressure (> > 20 torr) due to the collisional deactivation. The ratio of two products $(C_2ClF_3/C_2Cl_2F_2)$ decreased at low pressure (< 10 torr) and increased at high pressure (> 20 torr) with the increase of Ar pressure. The log-log plot of the reaction probability vs. laser pulse energy (${\\phi}$) was found to have a linear relationship, and its slope decreased as the added Ar pressure was increased. The reaction mechanisms for product formation have been suggested and validated by experimental evidences and considering the energetics. Fluorine-chlorine exchange reaction in the intermediate complex has been suggested to explain the formation of $C_2ClF_3$.

• Bulletin of the Korean Chemical Society
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• 제25권8호
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• pp.1217-1224
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• 2004

We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 ${\times}$1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond ($v_{HSi}$ =0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond.

• Bulletin of the Korean Chemical Society
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• 제24권7호
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• pp.986-992
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• 2003

We have calculated the probability of the OH formation and energy deposit of the reaction exothermicity in the newly formed OH, particularly in its vibrational motion, in the gas-surface reaction O(g) + H(ad)/Si → OH(g) + Si on the basis of the collision-induced Eley-Rideal mechanism. The reaction probability of the OH formation increases linearly with initial excitation of the HSi vibration. The translational and vibrational motions share most of the energy when the H-Si vibration is initially in the ground state. But, when the initial excitation increases, the vibrational energy of OH rises accordingly, while the energies shared by other motions vary only slightly. The product vibrational excitation is significant and the population distribution is inverted. Flow of energy between the reaction zone and the solid has been incorporated in trajectory calculations. The amount of energy propagated into the solid is only a few percent of the available energy released in the OH formation.

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.2873-2877
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• 2012

Quasi-classical trajectory (QCT) calculations of H+HLi reaction have been carried out on a new potential energy surface of the ground state reported by Prudente et al. [Chem. Phys. Lett. 2009, 474, 18]. The four polarization-dependent differential cross sections have been carried out in the center of mass (CM) frame at various collision energies. The reaction probability for the depletion channel has been studied over a wide collision energy range. It has been found that the collision energy decreases remarkably reaction probability, which shows the expected behavior of the title reaction belonging to an exothermic barrierless reaction. The results are in good agreement with previous RMP results. The P(${\theta}_r$), P(${\phi}_r$) and P(${\theta}_r,\;{\phi}_r$) distributions, the k-k'-j' correlation and the angular distribution of product rotational vectors are presented in the form of polar plots. The average rotational alignment factor <$P_2(j{\prime}{\cdot}k)$> as a function of collision energy is also calculated. The results indicate that the collision energy has a great influence on the polarization of the product rotational angular momentum vector j'.

• Bulletin of the Korean Chemical Society
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• 제26권9호
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• pp.1369-1380
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• 2005

The reaction of methyl radical with iodine molecule on an attractive potential energy surface is studied by classical trajectory procedures. The reaction occurs over a wide range of impact parameters with the majority of reactive events occurring in the backward rebound region on a subpicosecond scale. A small fraction of reactive events take place in the forward hemisphere on a longer time scale. The ensemble average of reaction times is 0.36 ps. The occurrence of reactive events is strongly favored when the incident radical and the target molecule align in the neighborhood of collinear geometry. Since the rotational velocity of I2 is slow, the preferential occurrence of reactive events at the collinear configuration of $CH_3{\ldots}I{\ldots}$I leads to the reaction exhibiting an anisotropic dependence on the orientation of $I_2$. During the collision, there is a rapid flow of energy from the $H_3C{\ldots}$I interaction to the I-I bond. The $CH_3I$ translation and $H_3C$-I vibration share nearly all the energy released in the reaction, and the distribution of the vibrational energy is statistical. The reaction probability is $\cong$0.4 at the $CH_3$ and I2 temperatures maintained at 1000 K and 300 K, respectively. The probability is weakly dependent on the $CH_3\;and\;I_2$ temperatures between 300 K and 1500 K.