• Bulletin of the Korean Chemical Society
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• 제19권10호
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• pp.1073-1079
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• 1998

The potential energy surface (PES) of the non-identical SN2 reactions, F- + CH3Cl → FCH3 + Cl and (H2O)F + CH3Cl → FCH3 + Cl-(H2O), were investigated with ab initio MO calculations. The ab initio minimum energy reaction path (MERP) of the F- + CH3Cl → FCH3 + Cl- was obtained and it was expressed with an intermediate variable t. The ab initio PES was obtained near around t. Analytical potential energy function (PEF) was determined as a function of the t in order to reproduce the ab initio PES. Based on Morse-type potential energy function, a Varying Repulsive Cores Model (VRCM) was proposed for the description of the bond forming and the bond breaking which occur simultaneously during the SN2 reaction. The MERP calculated with the PEF is well agreed with the ab initio MERP and PEF could reproduce the ab initio PES well. The potential parameters for the interactions between the gas phase molecules in the reactions and water were also obtained. ST2 type model was used for the water.

• EDISON SW 활용 경진대회 논문집
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• 제3회(2014년)
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• pp.1-13
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• 2014

Potential Energy Surface(PES)를 양자 계산을 통해 알아내는 것은 화학 반응을 이해하는 데에 큰 도움이 된다. 이를테면 Transition State(TS)의 configuration을 알 수 있고, 따라서 reaction path와 활성화 에너지 값을 예측하여, 진행시키고자 하는 화학반응의 이해를 도울 수 있다. 하지만 PES를 그리기 위해서는 해당 분자의 다양한 configuration에 대한 singlet point energy 계산이 필요하기 때문에, 계산적인 측면에서 많은 비용을 요구한다. 따라서 product와 reactant의 구조와 같은 critical point의 정보를 이용하여 최소한의 configuration을 sampling하여 전체 PES를 재구성하는 기계학습 알고리즘을 개발하여 다차원 PES 상에서의 화학반응의 예측을 가능하게 하고자 한다. 본 연구에서는 Barbaralane의 두 안정화 된 구조의 critical point로 하여 이 주변을 random normal distribution하여, B3LYP/6-31G(d) level의 DFT 계산을 통해 relaxed scanning하여 구조와 에너지를 구하였으며, 이 정보를 Support Vector Regression(SVR) 알고리즘을 적용하여 PES를 재구현하였으며, 반응경로와 TS의 구조 그리고 활성화 에너지를 구하였다. 또한 본 기계학습 알고리즘을 바닥상태에서 일어나는 반응이 아닌, 들뜬 상태와 전자 구조가 변하는 화학반응, avoid crossing, conical intersection과 같은 Non-adiabatic frame에서 일어나는 현상에 적용 가능성을 논하고자 한다.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3873-3879
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• 2011

The potential energy surface (PES) for the isomerizations and dissociations of the acrylonitrile radical cation was determined from the CBS-QB3 and CBS-APNO calculations. The Rice-Ramsperger-Kassel-Marcus model calculations were performed based on the PES in order to predict the competitions among the dissociation channels. The mechanisms for the loss of $H^{\bullet}$, $H_2$, $CN^{\bullet}$, HCN, and HNC were proposed. The $C_3H_2N^+$ ion formed by loss of $H^{\bullet}$ was predicted as a mixture of $CH{\equiv}C-C=NH^+$, $CH{\equiv}C-N{\equiv}CH^+$, and $CH_2=C-C{\equiv}N^+$. Furthermore $CH{\equiv}C-C{\equiv}N^{+{\bullet}}$ was formed mainly by a consecutive 1,2-H shift and 1,2-H2 elimination.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2301-2305
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• 2011

The potential energy surface (PES) for the loss of HCN or HNC from the pyrazine molecular ion was determined based on quantum chemical calculations using the G3//B3LYP method. Four possible dissociation pathways to form four $C_3H_3N^{+{{\bullet}}$ isomers were examined. A Rice-Ramsperger-Kassel-Marcus quasi-equilibrium theory model calculation was performed to predict the dissociation rate constant and the product branching ratio on the basis of the obtained PES. The resultant rate constant for the HCN loss agreed with the previous experimental result. The kinetic analysis predicted that the formation of $CH=CHN{\equiv}CH^{+{\bullet}}+HCN$ was predominant, which occurred by three consecutive steps, a C-C bond cleavage to form a linear intermediate, a rearrangement to form an H-bridged intermediate, and elimination of HCN.

• Bulletin of the Korean Chemical Society
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• 제35권10호
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• pp.3021-3024
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• 2014

The potential energy surface (PES) for the dissociation of the 2-hydroxypyridine (2-HP) radical cation was determined from G3//B3LYP calculations, including the loss of CO, HCN, and HNC. The formation of the 1H-pyrrole radical cation by decarbonylation through a more stable tautomer, the 2-pyridone (2-PY) radical cation, was the most favorable dissociation pathway. Kinetic analysis by the Rice-Ramsperger-Kassel-Marcus model calculations was carried out based on the obtained PES. It is proposed that the dissociation occurs after a rapid tautomerization to 2-$PY^{{\cdot}+}$, and that most of the ions generated by ionization of 2-HP have the structure of 2-$PY^{{\cdot}+}$ at equilibrium above the tautomerization barrier.

• Membrane and Water Treatment
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• 제6권1호
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• pp.1-13
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• 2015

The modification of ultrafiltration membranes with carbon nanotube (CNT) buckypaper on fouling control was investigated. Two types of commercially available flat-sheet membranes were used: PS35 and PES900C/D (PES) (the PS35 membranes were hydrophilic with a molecular weight cutoff of 20 kDa, and the PES membranes were hydrophobic with a molecular weight cutoff of 20 kDa). The CNT buckypaper modified ultrafiltration membranes were prepared by filtering a CNT suspension through the flat-sheet membrane in a dead-end ultrafiltration unit. After modification, the pure water flux of PES was significantly increased, while the pure water flux of PS35 was decreased. The properties of the CNT modified membranes were also investigated. Considering the antifouling properties, pure water flux of the modified membrane, and the stability of CNT buckypaper layer on the membrane surface, ethanol solution with a concentration of 50 wt.%, multi-walled carbon nanotubes (MWCNTs) with a larger diameter (30-50 nm), and the CNT loading with $7.5g/m^2$ was selected. The CNT buckypaper on the surface of ultrafiltration membranes can trap the pollutants in sewage effluent and prevent them reaching the surface of virgin membranes. Water quality analysis showed that the effluent quality of the modified membrane was obviously improved. The removal efficiency of humic acid and protein-like matters by the modified membrane was significant. These results indicate the potential application of the CNT buckypaper layer modified membranes in the field of wastewater reclaim.

• Bulletin of the Korean Chemical Society
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• 제33권12호
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• pp.4098-4102
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• 2012

The potential energy surface (PES) for the loss of HCN from the pyrimidine molecular ion has been explored using quantum chemical calculations. Possible reaction pathways to form five $C_3H_3N^{+{\bullet}}$ isomers have been obtained with Gaussian 4 model calculations. The rate constant for the HCN loss and the product branching ratio have been calculated using the Rice-Ramsperger-Kassel-Marcus theory on the basis of the obtained PES. The resultant rate constant agrees with the previous experimental result. By a kinetic analysis, it is proposed that the formation of $CH=CHC{\equiv}NH^{+{\bullet}}$ is favored near the dissociation threshold, while the formation of $CH=CHN{\equiv}CH^{+{\bullet}}$ is favored at high energies.

• 대한화학회지
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• 제28권3호
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• pp.155-162
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• 1984

메탄올-아세토니트릴 혼합용매계에서 파라치환된 브롬화 벤질 및 요오드화 벤질과 아닐린 치환체 사이의 친핵성 치환반응을 35.0$^{\circ}$C에서 연구하였다. Hammett관계식, Bronsted 관계식을 이용하여 반응 선택성 파라미터인$ {\rho}_N,\;{\rho}_C$ 및 ${\beta}$값을 구했으며 분광용매화 관계식의 계수 a, s 등을 구했다. 분광용매화 관계식의 계수 a, s 및 a/s값으로부터 혼합용매의 ${\pi}^{sat}$효과가 본 반응에 크게 작용함을 알았다. PES 모형을 적용하여 본 반응이 dissociative $S_N$2메카니즘으로 진행됨을 알 수 있었으며 이탈기 효과의 논의에는 PES모형이 실험결과와 잘 일치하지 않음을 알 수 있었다. 양자역학적 해석방법을 이용하여 본 반응의 전이상태 변화를 논의했으며 실험결과와 잘 일치함을 알 수 있었다.

• 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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• 제30권12호
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• pp.2973-2978
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• 2009

The decomposition reaction mechanism of $CH_3CF_2O$ radical formed from hydroflurocarbon, $CH_3CHF_2$ (HFC-152a) in the atmosphere has been investigated using ab-initio quantum mechanical methods. The geometries of the reactant, products and transition states involved in the decomposition pathways have been optimized and characterized at DFT-B3LYP and MP2 levels of theories using 6-311++G(d,p) basis set. Calculations have been carried out to observe the effect of basis sets on the optimized geometries of species involved. Single point energy calculations have been performed at QCISD(T) and CCSD(T) level of theories. Out of the two prominent decomposition channels considered viz., C-C bond scission and F-elimination, C-C bond scission is found to be the dominant path involving a barrier height of 12.3 kcal/mol whereas the F-elimination path involves that of a 28.0 kcal/mol. Using transition-state theory, rate constant for the most dominant decomposition pathway viz., C-C bond scission is calculated at 298 K and found to be 1.3 ${\times}$ 10$^4s{-1}$. Transition states are searched on the potential energy surfaces involving both decomposition channels and each of the transition states are characterized. The existence of transition states on the corresponding potential energy surface are ascertained by performing Intrinsic Reaction Coordinate (IRC) calculation.