• Bulletin of the Korean Chemical Society
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• v.25 no.9
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• pp.1397-1402
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• 2004

The vibrational predissociation of triatomic, i.e., atom-diatom, van der Waals complexes in transient electronic excited state has been widely investigated. The predissociation rates or lifetimes are major concerns of the previous studies. Experimentally rotational state distributions of diatomic product are hardly investigated and few theoretical stuides on rotational state distributions have appeared in literature. In this work, choosing the frequently studied $I_2(B)-Ne$ complex as an example, we investigate the change of rotational state distributions of $I_2(B)-Ne$ produced from predissociation of the various initial states of $I_2(B)-Ne$. The present study on the rotational distributions indicates that rotational state distributions depend significantly on the predissociation energy and the van der Waals vibrational modes of $I_2(B)-Ne$. That is, the initial state dependency of rotational state distributions is extensively discussed.

• Bulletin of the Korean Chemical Society
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• v.25 no.8
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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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• v.23 no.2
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• pp.229-240
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• 2002

Quantum mechanical calculation is performed for the $O(^1D)$ + HCl ${\rightarrow}$OH + Cl reaction using Reactive Infinite Order Sudden Approximation. Shifting approximation is also employed for the l ${\neq}$ 0 partial wave contributions. Various dynamical quantities are calculated and compared with available experimental results and quasiclassical trajectory results. Vibrational distributions agree well with experimental results i.e. product states mostly populated at $v_f$ = 3, 4. Our results also show small peak at $v_f$ = 0, which indicates bimodal vibrational distribution. The results show two significant broad peaks in ${\gamma}_i$ dependence of the cross section, one is at ${\gamma}_i$ = $15^{\circ}-35^{\circ}$ and the another is at ${\gamma}_i$= $55^{\circ}-75^{\circ}$ which can be explained as steric effects. At smaller gi, the distribution is peaked only at higher state ($v_f$ = 3, 4) while at the larger gi, both lower state ($v_f$ = 0) and higher state ($v_f$ = 3, 4) are significantly populated. Such two competing contributions (smaller and larger ${\gamma}_i$) result in the bimodal distribution. From these points we suggest two mechanisms underlying in current reaction system: one is that reaction occurs in a direct way, while the another is that reaction occurs in a indirect way.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.245-252
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• 2002

The computationally simple quantum mechanical method (VSCF-DWB-IOS) has been applied to studying the Ar-$CO_2$ vibrational predissociation phenomenon. The new methodology utilizes the vibrational self-consistent field method to determine the vibrational structure of the van der Waals complex, the distorted-wave Born approximation for dissociating process, and the infinite-order sudden approximation for the continuum dissociating product of $CO_2$. The dissociation due to the coupling of the symmetric stretching vibrational motion of $CO_2$ with the motion of the Ar van der Waals mode has been extensively investigated. The lifetimes of transient excited vibrational states, linewidths of absorption peak, and the rotational state distributions of the product, $CO_2$ have been computed. It has been found that the lifetime of the Ar-$CO_2$ in excited vibrational state is very long compared with that of triatomic van der Waals complexes and the product $CO_2$ carries a major portion of dissociation energy as a rotational energy.

• Bulletin of the Korean Chemical Society
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• v.16 no.12
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• pp.1193-1203
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• 1995

In this work, we focused on the setup of the tools for the analysis of the final rotational state distribution of photofragments in vibrational predissociations of triatomic van der Waals molecules A-B2. We found that reflection principle used for the direct photodissociation processes can also be applied to find out the final rotational state distributions for indirect photodissociation processes. The quantity which represents the strength of rovibrational coupling between the quasi-bound state and the final state is reflected into the mirror of the classical angular momentum function, instead of the initial state before light absorption used in the reflection principle of direct processes. The sign change in the first derivative of the interaction potential with respect to the bond distance of B2 is found to be the source of the binodal structures in the final rotational distributions of photofragments in the model system studied in this work. In MQDT analysis, short range eigenchannel basis functions were found to be localized in angle, in the previous work [Lee, C.W. Bull. Korean Chem. Soc. 1995, 16, 957.] and may be called angle functions. Angle functions enjoy simple geometrical structures which have simple functional relations with the final state distributions of photofragments. Two processes take place along the angle functions which resemble the quasi-bound state and dominate over other processes. Two such angle functions are found to be not only localized angularly but also localized either one of ends of B2 in motions along the bond of B2. These dominating photodissociation processes, however, cancel each other. This cancellation causes photodissociation to depend sensitively on the interaction potential at other angles than the dominant one. Part of potential surface where much larger torque exists can now play an important role in photodissociation. MQDT also enables us to see which processes play important roles after cancellation. This is done by examining the amounts of time delayed by asymptotic eigenchannels.

• Bulletin of the Korean Chemical Society
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• v.21 no.5
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• pp.493-496
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• 2000

By use of the rotational distribution expression previously derived based on the collisional time correlation function formalism, the rotational distributions of $CO_2$ vibrational ground state (00°0) after collisions with hot H, D, or Cl atom have been constructed. Energy and rotational quantum number parameters which can characterize the rotational distributions are also calculated and compared with those deduced from the experimental distribution. The results from this work would be very useful in predicting the rotational distributions in the lower J region for which experimental data are not available due to the interference from the ambient $CO_2$.

• Bulletin of the Korean Chemical Society
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• v.19 no.5
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• pp.539-544
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• 1998

A new theoretical method, named the SCF-DWB-IOS approximation, is suggested to investigate the vibrational predissociation of triatomic van der Waals complexes. The meta stable vibrational excited states are described with SCF (self-consistent-field) approximation and the fragmented diatomic continuum states are determined by using IOS (infinite order sudden) approximation. The dissociation process itself is studied by using DWB (distorted wave Born) approximation. As a test case, the predissociation rates, rotational state distributions of products, and the lifetimes of vibrationally excited states of $Ne-I_2$ are all computed which are in reasonable agreements with other theoretical and/or experimental results. The suggested SCF-DWB-IOS approximation scheme is found to be a very simple but efficient theoretical tool to investigate the vibrational predissociation dynamics of small van der Waals complexes.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1706-1712
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• 2014

The OH($X^2{\Pi}$, ${\upsilon}^{\prime\prime}=0,1$) internal state distribution following the reaction of electronically excited oxygen atom ($O(^1D_2)$) with cyclo-$C_3H_6$ has been measured using laser-induced fluorescence, and compared with that following the reaction of $O(^1D_2)$ with $C_3H_8$. The overall characteristics of the OH internal energy distributions for both reactions were qualitatively similar. The population propensity of the ${\Pi}(A^{\prime})$ ${\Lambda}$-doublet sub-level suggested that both reactions proceeded via an insertion/elimination mechanism. Bimodal rotational population distributions supported the existence of two parallel mechanisms for OH production, i.e., statistical insertion and nonstatistical insertion. However, detailed analysis revealed that, despite the higher exoergicity of the reaction, the rotational distribution of the OH following the reaction of $O(^1D_2)$ with $C_3H_8$ was significantly cooler than that with cyclo-$C_3H_6$, especially in the vibrational ground state. This observation was interpreted as the effect of the flexibility of the insertion complex and faster intramolecular vibrational relaxation (IVR).

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.429-434
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• 2009

The OH($X^2{\Pi},\;{\nu}$"=0, 1) internal state distributions from the reaction of electronically ground state oxygen atoms with HSi$Cl_3$ were measured using laser-induced fluorescence. The ground-state O$(^3P_J)$ atoms with kinetic energies above the reaction barrier were produced by photolysis of N$O_2$ at 355 nm. The OH product revealed strong vibrational population inversion, P(${\nu}$"=1)/P(${\nu}$"=0) = 4.0 ${\pm}$ 0.6, and rotational distributions in both vibrational states exhibit substantial rotational excitations to the limit of total available energy. However, no preferential populations in either of the two $\Lambda$ doublet states were observed from the micropopulations, which supports a mechanism involving a direct abstraction of hydrogen by the atomic oxygen. It was also found that the collision energy between O and HSi$Cl_3$ is effectively coupled into the excitation of the internal degrees of freedom of the OH product ($$ = 0.62, and $<\;f_{rot}>$ = 0.20). The dynamics appear consistent with expectations for the kinematically constrained reaction which supports the reaction type, heavy + light-heavy $\rightarrow$ heavy-light + heavy (H + LH′ $\rightarrow$ HL + H′). The dynamics of oxygen atom collision with HSi$Cl_3$ are discussed in comparison to those with Si$H_4$.

• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.644-648
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• 1995

Based on the collisional time correlation function (CTCF) formalism, Kim and Micha derived a simple expression which gives nascent rotational state distribution of molecules after collision with fast atoms.32 The expression is valid when the collision time is short and the collision is impulsive in nature. This expression has been applied to analyze the experimentally measured, state resolved rotational distribution of CO2 in various types of vibrational levels, i.e., (0001), (0111), (0002), and (1000/0200). The theoretical distributions obtained from this CTCF based expression can represent the experimentally measured rotational distributions remarkably well, and have been found to be much superior to those obtained from other simple theories such as Boltzmann distribution, prior distribution, breathing ellipsoid model, and phase space statistical calculation.