• Bulletin of the Korean Chemical Society
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• 제34권11호
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• pp.3265-3268
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• 2013

The multi-hydrogen bonded systems with the solvated electrons are investigated at the B3LYP/6-311++$G^{**}$ basis set level. The symmetrical linear geometrical characteristic is common for the dimer systems, while for the tetramer system, the tetrahedron configuration is generated. The NBO charge analyses demonstrate that the multi-hydrogen-multi-electron (mH-ne) coupling exist in these anion systems, as is supported by the electrostatic potential and the molecular orbital analyses. The positive chemical shift value of the central hydrogen ($H_c$) and the negative chemical shift value of the terminal hydrogen ($H_t$) indicate that the $H_c$ is electronegative while the $H_t$ is electropositive, respectively. Strong coupling between two central hydrogen atoms is demonstrated by the large spin-spin coupling constants. The solvated electron donates significant contributions for the stability of these systems.

• Bulletin of the Korean Chemical Society
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• 제24권6호
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• pp.802-804
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• 2003

The relative stabilities of weak binding clusters are sensitive to temperature due to the entropy effect. Thus, here we report significant changes in relative stabilities between two low-energy electron-water trimer structures and those between three low-energy electron-water pentamer structures, as the temperature increases. The trimer and pentamer show structural changes around 200 K.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1470-1474
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• 2009

Thermal and photochemistry of methyl iodide ($CH_3I)\;adsorbed\;on\;D_2O$ ice film on Cu(111) at 100 K were studied using temperature-programmed desorption (TPD) time-of-flight mass spectrometry (TOF-MS), X-ray and ultraviolet photoelectron spectroscopies. On the basis of TPD, multilayer and monolayer $CH_3I$ molecules desorb from $D_2O$ ice layer at 120 and 130 K, respectively. Photo-irradiation at 100 K exhibits dramatic changes in the TPD and I $3d_{5/2}\;XPS\;of\;CH_3I$ on ice film, due to a dramatic dissociation of $CH_3I$. The dissociation is likely activated by solvated electrons transferred from the metal substrate during photo-irradiation. No other photo-initiated reaction products were found within our instrumental detection limit. During photo-irradiation, the $CH_3I$, $CH_3$ and I could be trapped (or solvated) in ice film by rearrangement (and self-diffusion) of water molecules. A newly appeared parent molecular desorption peak at 145 K is attributed to trapped $CH_3I$. In addition, the $CH_3$ and I may diffuse through ice and chemisorb on Cu(111), indicated by TPD and I $d_{5/2}$ XPS taken with photo-irradiation time, respectively. No molecular ejection was found during photo-irradiation at 100 K. The work functions for $CH_3I/Cu(111),\;D_2O/Cu(111)\;and\;CH_3I/D_2$O/Cu(111) were all measured to be about 3.9 eV, 1.0 eV downward shift from that of clean Cu(111).

• Bulletin of the Korean Chemical Society
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• 제18권2호
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• pp.151-155
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• 1997

Stereochemical course of the reductive decyanation of two stereoisomeric 4-t-butyl-1-phenylcyclohexanecarbonitriles 3 and 4 using solvated electron has been studied. While sodium-mediated reactions of both 3 and 4 in the presence of alcohols give the same ratio, 1.5 : 1, in favor of the thermodynamically more stable product 5 over the other one 6, the ratios obtained from the potassium-mediated process are found to be very sensitive to the kind of H-donors. When reactions are performed without H-donors, 5 is only obtained from the experiments with both stereoisomers irrespective of the metal species.

• Bulletin of the Korean Chemical Society
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• 제33권6호
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• pp.1949-1954
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• 2012

We have developed a novel and eco-friendly synthetic route for the preparation of a two-dimensional layered zinc hydroxide with intercalated nitrate anions. The layered zinc hydroxide nitrate, called 'zinc basic salt', was, in general, successfully synthesized, using an electron beam irradiation technique. The 2-propanol solutions containing hydrated zinc nitrate were directly irradiated with an electron-beam at room temperature, under atmospheric conditions, without stabilizers or base molecules. Under electron beam irradiation, the reactive OH radicals were generated by radiolysis of water molecules in precursor metal salts. After further radiolytic processes, the hydroxyl anions might be formed by the reaction of solvated electrons and the OH radical. Finally, the $Zn_5(OH)_8(NO_3)_2{\cdot}2H_2O$ was precipitated by the reaction of zinc cation and hydroxyl anions. Structure and morphology of obtained compounds were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and high resolution transmission electron microscopy (HR-TEM). The chemical components of the products were determined by Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). The thermal behavior of products was studied by thermogravimetric (TG) and differential thermal analysis (DTA).

• Bulletin of the Korean Chemical Society
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• 제2권3호
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• pp.90-96
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• 1981

The significant structure theory of liquids has been successfully applied to the sodium ammonia solution. In applying the theory to sodium ammonia solution, we assumed there were four species in solution, i.e., sodium cation, solvated electron, triple ion, and free electron and equilibria existed between them. Based on these assumptions, we set up the model explaining the anomalous properties of sodium ammonia solution. The partition function for sodium ammonia solution is composed of the partition functions for the above four species and also for the Debye-Huckel excess free energy term. Agreements between calculated and experimental values of the thermodynamic quantities, such as molar volume, vapor pressure, partial molar enthalpy and entropy, and chemical potential as well as viscosity are quite satisfactory.

• Bulletin of the Korean Chemical Society
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• 제13권5호
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• pp.482-486
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• 1992

Ion-molecule reactions of acetylene and mixed acetylene-ammonia cluster ions are studied using an electron impact time-of-flight mass spectrometer. The present results clearly demonstrate that $(C_2H_2)_n^+$ cluster ion distribution represents a distinct magic number of n=3. The mass spectroscopic evidence for the enhanced structural stabilities of $[C_6H_4{\cdot}(NH_3)_m]^+$ (m=0-8) ions is also found along with the detection of mixed cluster $[(C_2H_2)_n{\cdot}(NH_3)_m]^+$ ions, which gives insight into the feasible structure of solvated ions. This is rationalized on the basis of the structural stability for acetylene clusters and the dissociation dynamics of the complex ion under the presence of solvent molecules.

• 대한화학회지
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• 제24권6호
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• pp.444-451
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• 1980

극성용매에서 전자의 용매화과정을 구체적으로 고찰하여 보기 위하여 테트라히드로퓨란(THF)-물 이성분계의 메디움효과를 측정하였다. 이 메디움효과는 Pt|$H_2Q$, Q, HCI, THF, $H_2O$|KC1 | $Hg_2Cl_2$|Hg(Pt) 셀로 수용액과 다른 용액(TGF-$H_2O$)에서 결정된 $H^+$ 이온에 대한 자유에너지 변화의 차(${\Delta}{\Delta}G_0$)를 이용하여 연구하였다. 여기서 $H_2Q$와 Q는 히드로퀴논과 퀴논을 각각 나타낸다. 자유에너지 변화의 차와 용매화된 전자의 최대흡수 에너지에 대한 용매의 유전상수 영향을 고찰하기 위하여 THF에서 $H_2O$의 회합정도를 관찰하였다. $H_2O$의 회합정도는 $H_2O$의 근적외선 스펙트럼을 이용하여 분석하였다. 이들 실험결과로부터 이성분 혼합용매에서 전자나 다른 이온의 용매화는 용매의 특정성분과 선택적으로 진행된다는 것을 알았다.

• Korean Chemical Engineering Research
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• 제49권2호
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• pp.263-270
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• 2011

본 논문의 목적은 리튬-암모니아 솔루션$(Li(NH_3)_n)$의 실험을 통하여 암모니아물질의 임계점인 $-40^{\circ}C$ 근처에서의 열전특성을 분석하고 이를 증명하는 것이다. 실험 결과 0.58 MPM~1.87 MPM을 갖는 리튬-암모니아 솔루션 $(Li(NH_3)_n)$ 은 온도차$({\Delta}T=0{\sim}15^{\circ}C)$에서 전류가 전압에 비례하는 열전전력을 발생시킨다는 사실을 확인하였다. 본 논문은 열전 물질 개발에 새로운 방향을 제시할 것이다.

• 한국수소및신에너지학회논문집
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• 제24권2호
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• pp.172-178
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• 2013

This study examined the electrochemical deposition and dissolution of lithium on nickel electrodes in 1 mol $dm^{-3}$ (M) $LiPF_6$ dissolved in propylene carbonate (PC) containing different 1,2-dimethoxyethane (DME) concentrations as a co-solvent. The DME concentration was found to have a significant effect on the reactions occurring at the electrode. The poor cycleability of the electrodes in the pure PC solution was improved considerably by adding small amounts of DME. This results suggested that the dendritic lithium growth could be suppressed by using co-solvents. After hundredth cycling in the 1 M $LiPF_6$/PC:DME (67:33) solution, almost no dead lithium has been found from the disassembled cell, resulting from suppression of dendritic lithium growth. Scanning electron microscopy revealed that dendritic lithium formation was greatly affected by the ratio of DME. Raman spectroscopy results suggested that the structure of solvated lithium ions is a crucial important factor in suppressing dendritic lithium formation.