• Title/Summary/Keyword: orbital order

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Kinetics and Stereochemistry of CO Substitution Reactions of Half-Open Chromocene Carbonyls(Ⅰ): Reactions of Cp($C_{5}H_{7}$)CrCO and Phosphines

  • Chung, Jong-Jae;Roh, Byung-Gill;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.14 no.2
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    • pp.207-211
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    • 1993
  • The CO substitution reactions in the complex, $Cp(S-C_5H_7)CrCO$ with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. From the reaction rates, it was suggested that the CO substitution reaction takes place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}\;=\;24.58\;kcal\;{\cdot}\;mol^{-1},\;{\Delta}S^{\neq}\;=\;3.05 cal\;{\cdot}\;mol^{-1}{\cdot}K^{-1}$. Unusually low value of ${\Delta}S^{\neq}$ suggests an ${\eta}^5-S\;{\to}\;{\eta}^5-U$ conversion of the pentadienyl ligand. This was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the total energy Of $Cp(S-C_5H_7)CrCO$ is about 6.84 kcal/mol more stable than that of $Cp(U-C_5H_7)CrCO$ and the energy of $[Cp(U-C_5H_7)CrCO^{\neq}$ transition state is about 4.25 kcal/mol lower than that of $[Cp(S-C_5H_7)Cr]^{\neq}$ transition state.

Electronic Structure Calculations for ArCO$_2\;^+$ and ArCO$_2$

  • Hwang, Woong-Lin;Lee, Yoon-Sup;Kim, Ja-Hong
    • Bulletin of the Korean Chemical Society
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    • v.9 no.3
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    • pp.153-156
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    • 1988
  • Ab initio calculations are performed for $ArCO_2^+$ and $ArCO_2$. Between the two configurations of $ArCO_2^+$ the orbital interactions and the higher order correlation calculations favor the T-shape, and their interaction energies are calculated to be approximately half the experimental values using 6-31G$^{\ast}$ basis set. In $ArCO_2$, the calculations qualitatively favor the T-structure, which is compatible with the experiment. However, the true interaction energy is obscured since it is within the BSSE limit at this basis set size and the correlation level. Addition of sp type diffuse functions increase the interaction energies by a considerable amount, but the BSSE estimated by CP method are responsible for the significant portion of the difference. The possible equilibrium structure of the $Ar^+-CO_2$ complex, where the charge is localized on Ar, is suggested as having a linear structure. The potential energy surface and the amount of charge transfer are shown to be sensitive to the type and balancing of basis set.

Geostationary Satellite Station Keeping Robustness to Loss of Ground Control

  • Woo, Hyung Je;Buckwalter, Bjorn
    • Journal of Astronomy and Space Sciences
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    • v.38 no.1
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    • pp.65-82
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    • 2021
  • For the vast majority of geostationary satellites currently in orbit, station keeping activities including orbit determination and maneuver planning and execution are ground-directed and dependent on the availability of ground-based satellite control personnel and facilities. However, a requirement linked to satellite autonomy and survivability in cases of interrupted ground support is often one of the stipulated provisions on the satellite platform design. It is especially important for a geostationary military-purposed satellite to remain within its designated orbital window, in order to provide reliable uninterrupted telecommunications services, in the absence of ground-based resources due to warfare or other disasters. In this paper we investigate factors affecting the robustness of a geostationary satellite's orbit in terms of the maximum duration the satellite's station keeping window can be maintained without ground intervention. By comparing simulations of orbit evolution, given different initial conditions and operations strategies, a variation of parameters study has been performed and we have analyzed which factors the duration is most sensitive to. This also provides valuable insights into which factors may be worth controlling by a military or civilian geostationary satellite operator. Our simulations show that the most beneficial factor for maximizing the time a satellite will remain in the station keeping window is the operational practice of pre-emptively loading East-West station keeping maneuvers for automatic execution on board the satellite should ground control capability be lost. The second most beneficial factor is using short station keeping maneuver cycle durations.

A Study on Electrostatic Discharging in Ultrapure and Electrolyzed Waters Using Kelvin's Thunderstorm Effect (캘빈방전 효과를 이용한 초순수 및 전해이온수의 정전기 방전 연구)

  • Kim, Hyung-won;Jung, Youn-won;Choi, In-sik;Choi, Byung-sun;Choi, Donghyeon;Ryoo, Kun-kul
    • Journal of the Semiconductor & Display Technology
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    • v.21 no.1
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    • pp.5-11
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    • 2022
  • Despite the increasing importance of manufacturing and application R&D for ultrapure deionized water and electrolyzed ion water, various and systematic studies have not been conducted until now. In this study, the electrostatic discharge (ESD) behavior of electrolyzed ion water using a proton exchange membrane(PEM) was evaluated according to the type, flow rate, and bubble of electrolyzed ion water. In addition, by observing that Oxidation Reduction Potential (ORP) value returns to the unique value of electrolyzed ion water after electrostatic discharge, the possibility of two types of ions participating in electrostatic discharge ((H2O)n+ (assumed)) and ions for maintaining the characteristics of electrolyzed water could be inferred. In order to confirm the chemical structure and characteristics of the cations, in-depth research related to water molecular orbital energy or band gap should be followed.

Variations of Biogenic Components in the Region off the Lutzow-Holm Bay, East Antarctica during the Last 700 Kyr (지난 70만 년 동안 동남극 Lutzow-Holm만 주변 해역의 생물기원 퇴적물 함량 변화)

  • Kim, Yeo-Hun;Katsuki, Kota;Suganuma, Yusuke;Ikehara, Minoru;Khim, Boo-Keun
    • Ocean and Polar Research
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    • v.33 no.3
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    • pp.211-221
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    • 2011
  • Contents of biogenic components [opal, $CaCO_3$, TOC (total organic carbon)] were measured in Core LHB-3PC sediments collected off Lutzow-Holm Bay, in order to understand glacial-interglacial cyclic variation of the high-latitude surface-water paleoproductivity, in the Indian Sector of the Southern Ocean. An age model was established from the correlation of ARM/IRM ratios of Core LHB-3PC with LR04 stack benthic ${\delta}^{18}O$ records, in complement with radiocarbon isotope ages and biostratigraphic Last Appearance Datum (LAD). The core-bottom age was estimated to be about 700 ka. Although the $CaCO_3$ content is very low less than 1.0% throughout the core, the opal and TOC contents show clear glacial-interglacial cyclic variation such that they are high during the interglacial periods (7.2-50.3% and 0.05-1.00%, respectively) and low during the glacial periods (5.2-25.2% and 0.01-0.68%, respectively). According to the spectral analysis, the variation of opal content is controlled mainly by eccentricity forcing and subsequently by obliquity forcing during the last 700 kyrs. The opal contents of Core LHB-3PC also represent the apparent Mid-Pleistocene Transition (MPT)-related climatic variation in the glacial-interglacial cycles. In particular, the orbital variation of the opal contents shows increasing amplitudes since marine isotope stage (MIS) 11, which defines one of the important paleoclimatic events during the late Quaternary, called the "Mid-Brunhes Event". Based on the variation of the opal contents in Core LHB-3PC, we suggest that the surface-water paleoproductivity in the Indian Sector of the Southern Ocean followed the orbital (glacial-interglacial) cycles, and was controlled mainly by the extent of sea ice distribution during the last 700 kyrs.

A Study on Legal Issues in Telecommunication and Direct Broadcasting by Uses of Artificial Satellites (정보화(情報化) 시대(時代)에서의 통신(通信) 및 방송위성이용(放送衛星利用)에 따르는 법적(法的) 문제(問題) 분석(分析)과 대응방안 연구(硏究))

  • Lee, Young-Jin
    • The Korean Journal of Air & Space Law and Policy
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    • v.9
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    • pp.445-488
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    • 1997
  • In the forthcoming 21st century new technical and scientific developments in outer space demands new approaches towards the problems arising in several fields of the use and exploitation of outer space including practical applications. The main purposes of this study are to analyze the legal problems of geostationary orbital position, telecommunication, direct television broadcasting by uses of artificial satellites. Communication via artificial Earth satellites was one of the first applications of space technology and is now one of the most developed field. From the technical and economic standpoints the advantages of world-wide satellites communication system are too all obvious. However, as the practical uses of space technology become more freguent, the legal conflicts among nations have become more divisive. One of the problem grown in uses of artificial satellites is that of the increasing shortage of suitable orbital slot positions for satellites, especially in geostationary orbit. Legal status of geostationary orbit as a limited resourece have to be reviewed in consideration of the side effect of the "First use, first-served" principle. The geostationary orbit is to be used for the benifits of all mankind and to be guaranteed for each state institutionaly in order to have eguitable access to the use of the orbit. Rapid increase of satellites broadcasting system in not only developed countries but also in developing countries opened up new possibilities with one another's scientific and cultural achievements. But there is also a potential danger that this powerful new instrument of influencing public opinion will be abused. Such a danger incudes spill-over or harmful interference. This controversial issue brings about the question whether prior consent from the receiver nation is needed to broadcast across international boundaries. Some states have rejected prior consent because it interfere with the free flow of information. Many other countries have opposed that opinion as an invasion and violation of sovereignty and as a violation of the 1967 Treaty and the UN Charter. Since declaration of the First Year of Outer Space in 1985, our country have promoted the plan of launching communication and broadcasting satellites. With the Koreasat launched in 1995 as the start, a real satellite-telecommunication era was opened in korea. According to this new development of our country, there will also rise various legal problems related to satellite broadcasting and telecommunication such as the inflow of foreign programs, the permeation of culture and the infringement of program copyright. Consequently the effective reactions to these problems in satellite-communication era should be tried including international cooperation. It is therefore to take into careful consideration the legal issues which may arise in outer space activities and to formulate positive policy on international cooperation with surrounding or advanced countries and international organization concerned. For this purpose the United Nations also prepares the UNISPACE III in 1999, to enable the international community to meet a more promising 21st century.

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V700 Cygni: A Dynamically Active W UMa-type Binary Star II

  • Kim, Chun-Hwey;Jeong, Jang-Hae
    • Journal of Astronomy and Space Sciences
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    • v.29 no.2
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    • pp.151-161
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    • 2012
  • An intensive analysis of 148 timings of V700 Cyg was performed, including our new timings and 59 timings calculated from the super wide angle search for planets (SWASP) observations, and the dynamical evidence of the W UMa W subtype binary was examined. It was found that the orbital period of the system has varied over approximately $66^y$ in two complicated cyclical components superposed on a weak upward parabolic path. The orbital period secularly increased at a rate of $+8.7({\pm}3.4){\times}10^{-9}$ day/year, which is one order of magnitude lower than those obtained by previous investigators. The small secular period increase is interpreted as a combination of both angular momentum loss (due to magnetic braking) and mass-transfer from the less massive component to the more massive component. One cyclical component had a $20.^y3$ period with an amplitude of $0.^d0037$, and the other had a $62.^y8$ period with an amplitude of $0.^d0258$. The components had an approximate 1:3 relation between their periods and a 1:7 ratio between their amplitudes. Two plausible mechanisms (i.e., the light-time effects [LTEs] caused by the presence of additional bodies and the Applegate model) were considered as possible explanations for the cyclical components. Based on the LTE interpretation, the minimum masses of 0.29 $M_{\odot}$ for the shorter period and 0.50 $M_{\odot}$ for the longer one were calculated. The total light contributions were within 5%, which was in agreement with the 3% third-light obtained from the light curve synthesis performed by Yang & Dai (2009). The Applegate model parameters show that the root mean square luminosity variations (relative to the luminosities of the eclipsing components) are 3 times smaller than the nominal value (${\Delta}L/L_{p,s}{\approx}0.1$), indicating that the variations are hardly detectable from the light curves. Presently, the LTE interpretation (due to the third and fourth stars) is preferred as the possible cause of the two cycling period changes. A possible evolutionary implication for the V700 Cyg system is discussed.

Transmission of Substituent Effects through 5-Membered Heteroaromatic Rings

  • Lee, Ik Hun;Ri, Sun Gi;Kim, Chang Gon;Jeong, Dong Su;Kim, Chan Gyeong
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.882-890
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    • 2000
  • Ab initio calculations are carried out on protonation equilibria of 5-memberedheteroaromatic aldehydes (5MHAs;heteroatom Y = NH, O, PH,and S and substituentZ = NH2, OCH3, SCH3, CH3, H, Cl, CHO, CN,NO2) at the $MP2}6-31G*$ level. Naturalbond orbital (NBO) analyses show that the optimal localized natural Lewis structures of the protonated aldehydes,(P), are ortho (C3) protonated (for Y = O, PH and S) and N-pro-tonated (for Y = NH) forms in contrast to the standard structural Lewis formula for aldehydes, (R). The delo-calizability of ${\pilone}-pairon$ the heteroatom $(n{\pi}(Y))$ is in the order Y = NH > O > S > PH. The transmission efficiency of (Z) substituent effects to the carbonyl moiety run parallel to the delocalizability of $n{\pi}(Y)$ for R,but is dominantly influenced by the cationic charge on $C{\alpha}(C{\alpha}+)$ for P, which is in the reverse order of thede-localizability of $n{\pi}(Y).$ The Hammett ${\rho}values$ for variation of Z in the protonation are determined by the dif-ference in the transmission efficiencies between Pand R stateat simple interpretation of their magnitude is not warranted. However,the magnitude of the gas-phase ${\rho}z+$ values decreases as the level ofcomputation is raised from RHF/3-21G* to RHF/6-31G* and to $MP2}6-31G*$ but increases again at the MP4SDQ/6-31G* level. Further decrease occurs when solvent effect (water) is accounted for by the SCRF method. Comparison of the SCRF ${\rho}z+values$ with those determined in the aqueous acid solution for Y = S and CHCH shows inadequacy of accounting for the solvent effects on the ${\rho}values$ by a continuum model. It is noteworthy that semiempirical calculations, especially theAM1 method, give even lower magnitude of the gas-phase ${\rho}values.

Kinetics and Stereochemistry of CO Substitution Reactions of Half-Open Chromocene Carbonyls(Ⅲ): Reactions of $Cp^{*}(\eta^{5}-C_{5}H_{7})$CrCO and Phosphines

  • Jong-Jae Chung;Byung-Gill Roh;Yu-Chul Park
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.549-554
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    • 1993
  • The CO substitution reactions in the complex, $Cp^*(C_5H_7)$CrCO with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. For the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}= 21.99{\pm}2.4$ kcal/mol, ${\Delta}S^{\neq}= 8.9{\pm}7.1$ cal/mol·k. Unusually low value of ${\Delta}S^{\neq}$, suggested an ${\eta}^5-S{\to}\;{\eta}^5$-U conversion of the pentadienyl ligand. At various temperature, the rates of reaction for the Cp(pdl)CrCO complexes increase in the order $Cp^*(C_5H_7)$-CrCO < Cp$(C_5H_7)$CrCO < Cp(2,4-$C_5H_{11}$)CrCO, which can be attributed to the usual steric acceration or electronic influence for the ligand substitution of metal complexes. This suggestion was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the energy of $[Cp^*(U-C_5H_7)Cr]^{\neq}$ transition state is about 4.93 kcal/mol lower than that of [Cp(S-$C_5H_7)Cr]^{\neq}$ transition state, and the arrangement of the overlap populations between Cr and the carbon of CO is $Cp^*(C_5H_7)$CrCO > Cp($C_5H_7$)CrCO > Cp(2,4-$C_7H_{11}$)CrCO.

A study of the frequency and characteristics of minor clinical manifestations in children with atopic dermatitis (소아 아토피피부염 환자의 부증상 빈도 및 특징에 대한 연구)

  • Cho, Ji Eun;Jeon, You Hoon;Yang, Hyeon Jong;Pyun, Bok Yang
    • Clinical and Experimental Pediatrics
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    • v.52 no.7
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    • pp.818-823
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    • 2009
  • Purpose : We aimed to evaluate the frequency and characteristics of minor clinical manifestations of atopic dermatitis (AD) in Korean children to aid the diagnosis and treatment of AD. Methods : From April 2007 to December 2007, we enrolled 106 children (aged 1 month [infants] to 15 years) diagnosed with AD at the Pediatric Allergy Respiratory Center in Soonchunhyang University Hospital. Clinical manifestations were examined and laboratory findings (total and specific immunoglobulin E [IgE] levels and peripheral blood eosinophil count) were analyzed and compared. Results : Minor symptoms, in order of frequency, included xerosis (78.3%), aggravation due to environmental or emotional stress (43.4%), lichenification (35.8%), orbital darkening (34.0%), periauricular eczema (33.0%), and cutaneous infection (31.1%). Older children (${\geq}2$ years) showed more orbital darkening (P=0.01), horizontal crease (P=0.01), and lichenification (P=0.001) than infants. Patients with severe AD (scoring atopic dermatitis [SCORAD] score, ${\geq}40$) showed higher frequencies of xerosis (P= 0.04), cutaneous infection (P=0.03), ichthyosis (P=0.18), keratosis pilaris (P=0.02), pityriasis alba (P=0.07), recurrent conjunctivitis (P=0.02), orbital darkening (P=0.001), aggravation due to environmental or emotional stress (P=0.05), facial eczema (P=0.001), lichenification (P=0.001), and hand/foot eczema (P=0.04) than those with mild-to-moderate AD. Children with atopic eczema showed more facial eczema (P=0.01) and lichenification (P=0.04) than those with non-atopic eczema. Conclusion : The clinical manifestations of AD were similar to those established by Hanifin and Rajka. However, we need to develop our own diagnostic criteria for AD, because the frequencies shown by our subjects differed from those observed in other countries.