• Title/Summary/Keyword: Transition state theory

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Statistical Analysis of Random Parameter Systems with Perturbation Method (퍼터베이션 방법을 이용한 랜덤 파라미터 시스템의 통계적 해석)

  • 김영균
    • Journal of the Korean Institute of Telematics and Electronics
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    • v.19 no.2
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    • pp.1-6
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    • 1982
  • This paper reviews and describes some applications of perturbation theory in the practical analysis of linear systems which involve random parameters. Statistical measures of the system outputs are derived in terms of statistical measures of the system parameters and inputs (i.e., in the way of perturbed linear operator equations). Perturbed state transition matrix is also derived. With simple first-order and second-order linear system models, we compare the accuracy of perturbation results with the exact ones. And the convergence of perturbation series is also investigated.

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Determination of Reactivity by MO Theory (XXXIV). MINDO/3 Theoretical Studies on Sigmatropic Hydrogen Rearrangements (1) : Systems with Central Carbon Atom (분자궤도론에 의한 반응성 결정 (제34보). 수소 시그마 결합 자리옮김 반응에 대한 MINDO/3 이론연구 (1) : 중앙탄소원자를 가진 계)

  • Cho, Jeoung-Ki;Lee, Ik-Choon;Oh, Hyuck-Keun;Cho, In-Ho
    • Journal of the Korean Chemical Society
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    • v.28 no.4
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    • pp.217-230
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    • 1984
  • The MINDO/3 method was used in determination of transition states and activation barriers for various 1,2-, 1,3- and 1,5-sigmatropic hydrogen rearrangements involving systems with central carbon atom. It was found that, besides the consideration of orbital symmetry, steric effect, aromaticity, and orbital interactions were found to dictate the stability of the transition state. For systems with hetero atoms, lone pair orbitals tend to ease orbital distortion required at the transition state by participating in hydrogen transfer process and were found to lower the activation barrier accordingly. Comparison of the relative barrier heights with those obtained by using more sophisticated ab initio MO calculations showed that the MINDO/3 results give qualitatively the same tendency of the relative order of the activation barriers.

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Experience of Poverty Exit across Generations (빈곤의 세대간 탈피 경험)

  • Kim, Kyo-seong;Noh, Hye-jin
    • Korean Journal of Social Welfare Studies
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    • v.42 no.1
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    • pp.243-278
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    • 2011
  • The main purpose of this paper is to understand the process of the poverty exit across generations through the live experience based on the grounded theory analysis of the in-depth interview. We find that poverty means a lack of achievement and freedom of agency that is a level of control about resource and situation. So exit of poverty across generations is the state that is not only to achieve functioning but also to recover capabilities. Based on this result, central phenomena of the intergenerational exit process of poverty are support from relation and continuous transition at each stage in life. Even if this central phenomenon is an important event, it has the incomplete attribute. Because support from relation is beyond individual scope of control and participants can't escape second labor market as they don't have enough time in the process of transition. Therefore, this paper suggests that the expansion of state welfare and strategy should support transition as policy priorities to minimize limitation of relation and risk of income loss.

The Impact of Ownership Structure on Listed Firms' Performance in Vietnam

  • VO, Dut Van;TRAN, Truc Viet Thanh;DANG, Nga Thi Phuong
    • The Journal of Asian Finance, Economics and Business
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    • v.7 no.11
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    • pp.195-204
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    • 2020
  • The aim of this study is to estimate the impact of ownership structure on the performance of listed firms in transition economy. Buiding upon agency theory, hypotheses on such relationship are proposed. A detailed panel data of 502 non-financial companies listed on Ho Chi Minh Stock Exchange and Hanoi Stock Exchange over the period from 2013 to 2018, and the system generalized method of moment estimation are employed to test the proposed hypotheses. To ensure the reliability of data, this study excludes companies that violate information disclosure regulations or that are subject to special supervision by the State Securities Commission of Vietnam. Some firms with inadequate information, firms that lack the financial data required for creating variable or firms that have inconsistent construction are also re-screened. We only collect the data of enterprises that have ownership structure of two or more components. Estimation results reveal that state ownership has an U-shaped relationship with the performance of Vietnamese listed firms, while foreign ownership and the degree of ownership concentration have an inverted U-shaped relationship with listed firms' performance. The article provides governance implications that Vietnamese listed firms should decrease state ownership and foreign ownership to improve firm performance in order to boost investors' confidence.

Ab Initio Study of Mechanism of Forming Spiro-Ge-Heterocyclic Ring Compound From C2Ge=Ge: and Formaldehyde

  • Lu, Xiuhui;Li, Yongqing;Ming, Jingjing
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3690-3694
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    • 2013
  • The $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) is a new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet state Cl2Ge=Ge: and formaldehyde has been investigated with CCSD(T)//MP2/$6-31G^*$ method. From the potential energy profile, it could be predicted that the reaction has only one dominant reaction pathway. The reaction rule presented is that the two reactants first form a fourmembered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the ${\pi}$ orbital of formaldehyde forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge: atom in intermediate hybridizes to an $sp^3$ hybrid orbital after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between $H_2Ge=Ge:$ and formaldehyde, and laid the theory foundation of the cycloaddition reaction between $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) and asymmetric ${\pi}$-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds. The study extends research area and enriches the research content of germylene chemistry.

Computational Study on OH and Cl Initiated Oxidation of 2,2,2-Trifluoroethyl Trifluoroacetate (CF3C(O)OCH2CF3)

  • Singh, Hari Ji;Tiwari, Laxmi;Rao, Pradeep Kumar
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1385-1390
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    • 2014
  • Hydrofluoroethers (HFEs) are developed as a suitable for the replacement of environmentally hazardous CFCs and are termed as third generation refrigerants. One of the major products of decomposition of HFEs in the atmosphere is a fluoroester. The present study relates to the OH and Cl initiated oxidation of $CF_3C(O)OCH_2CF_3$ formed from the oxidation of HFE-356mff. The latter is used as a solvent in the industry and reaches the atmosphere without any degradation. Kinetics of the titled molecule has been studied at MPWB1K/6-31+G(d,p) level of theory. Single point energy calculations have been made at G2(MP2) level of theory and barrier heights are determined. The rate constants are calculated using canonical transition state theory. Tunnelling correction are made using one-dimensional Eckart potential barrier. The rate constant calculated during the present study are compared with the experimental values determined using relative rate method and FTIR detection technique.

Corporate Social Responsibility in Modern Transnational Corporations

  • Vitalii Nahornyi;Alona Tiurina;Olha Ruban;Tetiana Khletytska;Vitalii Litvinov
    • International Journal of Computer Science & Network Security
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    • v.24 no.5
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    • pp.172-180
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    • 2024
  • Since the beginning of 2015, corporate social responsibility (CSR) models have been changing in connection with the trend towards the transition of joint value creation of corporate activities and consideration of stakeholders' interests. The purpose of the academic paper lies in empirically studying the current practice of social responsibility of transnational corporations (TNCs). The research methodology has combined the method of qualitative analysis, the method of cases of agricultural holdings in emerging markets within the framework of resource theory, institutional theory and stakeholders' theory. The results show that the practice of CSR is integrated into the strategy of sustainable development of TNCs, which determine the methods, techniques and forms of communication, as well as areas of stakeholders' responsibility. The internal practice of CSR is aimed at developing norms and standards of moral behaviour with stakeholders in order to maximize economic and social goals. Economic goals are focused not only on making a profit, but also on minimizing costs due to the potential risks of corruption, fraud, conflict of interest. The system of corporate social responsibility of modern TNCs is clearly regulated by internal documents that define the list of interested parties and stakeholders, their areas of responsibility, greatly simplifying the processes of cooperation and responsibility. As a result, corporations form their own internal institutional environment. Ethical norms help to avoid the risks of opportunistic behaviour of personnel, conflicts of interest, cases of bribery, corruption, and fraud. The theoretical value of the research lies in supplementing the theory of CSR in the context of the importance of a complex, systematic approach to integrating the theory of resources, institutional theory, theory of stakeholders in the development of strategies for sustainable development of TNCs, the practice of corporate governance and social responsibility.

Potential Energy Surfaces for Ligand Exchange Reactions of Square Planar Diamagnetic PtY2L2 Complexes:Hydrogen Bond (PtY2L2···L') versus Apical (Y2L2Pt···L') Interaction

  • Park, Jong-Keun;Kim, Bong-Gon
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1405-1417
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    • 2006
  • The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum $(PtY_2L_2\;:\;Y,\;L=Cl^-,\;OH^-,\;OH_2,\;NH_3)$ complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of $(PtCl_4\;+\;H_2O)^{^\ast_\ast}\;to\;[PtCl_3(H_2O)\;+\;Cl^-]$ and $[Pt(NH_3)_2Cl_2\;+\;H_2O]$$[Pt(NH_3)_2Cl_2\;+\;H_2O]$ to $[Pt(NH_3)_2Cl(H_2O)\;+\;Cl^-] $ were investigated in detail. For these two exchange reactions, the transition states $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime])^{^\ast_\ast} $ correspond to complexes such as $(PtCl_4{\cdot}{\cdot}{\cdot}H_2O)^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$, respectively. In the transition state, $([PtCl_4{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]]^{^\ast_\ast})$ have a kind of 6-membered $(Pt-Cl{\cdot}{\cdot}{\cdot}HOH{\cdot}{\cdot}{\cdot}Cl)$ and $(Pt-OH{\cdot}{\cdot}{\cdot}Cl{\cdot}{\cdot}{\cdot}HN)$ interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving $Cl^-$ and an entering $H_2O$. Simultaneously, the entering $H_2O$ interacts with a leaving $Cl^-$. No vertical one metal-ligand interactions $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime]) $ are found at the axial positions of the square planar $(PtY_2L_2)$ complexes, which were formed via a vertically associative mechanism leading to $D_{3h}$ or $C_{2v}$-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtCl4(H2O)n(n=2,4)} into {$PtCl_3(H_2O)_{(n-2)}\;+\;Cl^-(H_2O)_2$} and the binding energies {$PtCl_4(H_2O)_n$(n = 1-5)} of $PtCl_4$ with water molecules are drawn.

Analysis of Successional Trend by Transition Matrix Model in the Mixed Broadleaved-Abies Forest of Mt. Odae (추이행렬(推移行列) 모델에 의한 오대산(五臺山) 활엽수(闊葉樹)-젓나무속(屬) 혼효림(混淆林)의 천이(遷移) 경향(傾向) 분석(分析))

  • Kim, Ji Hong
    • Journal of Korean Society of Forest Science
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    • v.81 no.4
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    • pp.325-336
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    • 1992
  • The successional status and potential natural vegetation were examined in a mixed broadleaved-Abies forest located at Mt, Odae National Park. The examination was based on the subsequent process of generation replacement by understory saplings for the dominant canopy trees within 88 $5m{\times}50m$ belt transects. The transition matrix model, which was modified from mathematical theory of Markov chain, was employed to analyze the successional status of the study forest. The model suggests that the study forest is still seral, and it is considered to be more than 700 years away from the steady state or climax in terms of species composition. The simulations predict a remarkable decrease in the proportion of species composition of the present dominant Quercus mongolica and Tilia amurensi.s from current 28% and 13% to less than 3% and 5%, respectively, at the steady state. On the contrary, the proportions of Abies holophylla, Acer pseudo-sieboldianum, Carpinus cordata, and Pinus koraiensis will increase at the steady state. The ratio of mixture between deciduous and coniferous trees will be gradually changed from current 6.5 : 3.5 to 5.0 : 5.0 at equilibrium. Discussion for the problems of Quercus mongolica in successional status noted that the species behaved as a mid-successional dominant, not a climax species in the study forest. The hypothesis and sensitivity of the transition matrix model were also discussed to evaluate the applicability to the real situation. The overall results indicated that the present dynamics of the forest must reflect the seral state due to previous disturbance mainly by hyman related interference.

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Density Functional Study on the C-H Bond Cleavage of Aldimine by a Rhodium(I) Catalyst

  • Yoo, Kyung-Hwa;Jun, Chul-Ho;Choi, Cheol-Ho;Sim, Eun-Ji
    • Bulletin of the Korean Chemical Society
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    • v.29 no.10
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    • pp.1920-1926
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    • 2008
  • We investigated the C-H bond activation mechanism of aldimine by the [RhCl$(PPH_3)_3$] model catalyst using DFT B3LYP//SBKJC/6-31G*/6-31G on GAMESS. Due to their potential utility in organic synthesis, C-H bond activation is one of the most active research fields in organic and organometallic chemistry. C-H bond activation by a transition metal catalyst can be classified into two types of mechanisms: direct C-H bond cleavage by the metal catalyst or a multi-step mechanism via a tetrahedral transition state. There are three structural isomers of [RhCl$(PH_3)_2$] coordinated aldimine that differ in the position of chloride with respect to the molecular plane. By comparing activation energies of the overall reaction pathways that the three isomeric structures follow in each mechanism, we found that the C-H bond activation of aldimine by the [RhCl$(PH_3)_3$] catalyst occurs through the tetrahedral intermediate.