• Bulletin of the Korean Chemical Society
• /
• v.29 no.2
• /
• pp.438-444
• /
• 2008

A self-assembled monolayer of 2,2'-bipyridine (22BPY) molecules on Au(111) underwent a structural phase transition when the polarity of a bias voltage was switched in scanning tunneling microscopy (STM) experiments. The nature of two bright spots representing each 22BPY molecule on Au(111) in the high-resolution STM images was identified by calculating the partial density plots for a monolayer of 22BPY molecules adsorbed on Au(111) using tight-binding electronic structure calculations. The stacking pattern of the chains of 22BPY molecules on Au(111) was explained by examining the intermolecular interactions between the 22BPY molecules based on first principles electronic structure calculations for a 22BPY dimer, (22BPY)2. The structural instability of the 22BPY molecule arrangement caused by a change in the bias voltage switch was investigated by estimating the adsorbate-surface interaction energy using a point-charge approximation for Au(111).

• Bulletin of the Korean Chemical Society
• /
• v.29 no.7
• /
• pp.1327-1331
• /
• 2008

Novel $CO_2$-soluble 8-hydroxyquinoline (8-HQ) chelating agents were synthesized and evaluated for solubility and metal ion extraction ability in supercritical $CO_2\;(Sc-CO_2)$. Among them, secondary amide-containing 8- HQ derivatives cannot be dispersed well into Sc-$CO_2$, but tertiary amide-containing derivatives can dissolve completely in Sc-$CO_2$ even at low CO2 pressures, perhaps owing to the predominant intermolecular interaction between the chelating agent and the $CO_2$ molecule. Based on 8-HQ chelating agent solubility data, we investigated the extraction of metal ions ($Co^{2+}$, $Cu^{2+}$, $Sr^{2+}$, $Cd^{2+}$, and $Zn^{2+}$) using two highly $CO_2$-soluble 8-HQ derivatives (4d, 4e) in Sc-$CO_2$. The extraction efficiency of tertiary amide-containing 8-HQ ligands, both fluorinated and non-fluorinated forms, was dramatically increased in the presence of diethyl amine (organic base). We suggest that diethyl amine could play an important synergistic role in the stronger metal binding ability of 8-HQ through an in situ deprotonation reaction in Sc-$CO_2$ medium.

• Korean Journal of Crystallography
• /
• v.1 no.1
• /
• pp.14-18
• /
• 1990

Econazole nitrate, 1-{2-[(4-chlorophenyl)methoxy]-2-(2,4-dichlorophenyl) ethy1}-1H-imidazole mono-nitrate.C18 H16 CI13 N3 O4 Mw=444.7 Monoclinic P/2₁c,a=17.337(4)A, b=15.191(5), c=7.601(3)A, β=91.72(2)', V=2000.9A3, Z=4, Dc=1.49g/cm3, Dm=1.45g/cm3(mo-ka)= 0.7107A, μ=4.31cm-1, F(000)=912.0, T=298'K, final R=0.061 for 1330 unique observed reflection. Each of the three ring system for the stars with B,A and C ring in order whilst A and C ring of econazole lie close to the same plane which is nearly 60˚with B ring. The hydrogen binding nitrogen of C ring and oxygen of nitrate contributes to stailization of econazole nitrate. Intr and intermolecular distances and angles are within the values recorded for simiar compounds.

• Polymer(Korea)
• /
• v.26 no.6
• /
• pp.767-777
• /
• 2002

In this work, biodegradable modified aliphatic polyester (MAP) in tetrafunctional epoxy (4EP) resin was investigated in terms of cure kinetics, thermal stabilities, rheological properties, and mechanical interfacial properties. DSC results of the blends show that the cure activation energies (E$\_$a/) were increased in 10 wt% of MAP compared with neat 4EP, due to the increasing intermolecular interaction between 4EP and MAP. The decomposed activation energies (E$\_$t/) derived from Coats-Redfern method, were increased within the 10∼30 wt% composition range of MAP contents, resulting from increasing the cross-linking density of the blend system. Rheological properties of the blend system were investigated under isothermal condition using a rheometer. Cross-linking activation energies (E$\_$c/) were determined from the Arrhenius equation based on gel time and curing temperature. As a result, the E$\_$c/ showed a similar behavior with E$\_$a/. The fracture toughness (K$\_$IC/) of the mechanical interfacial properties was discussed in semi-IPN behaviors of the casting specimen.

• Journal of Integrative Natural Science
• /
• v.3 no.4
• /
• pp.226-230
• /
• 2010

Calculation of partial charge is important in chemistry. However, because there are many methods developed, it is of considerable interest to know how to calculate and apply properly to address various chemical problems. For basis set, usually double zeta quality is acceptable, and double zeta polarization function would be enough for most cases. To describe electronic state more accurately, Many electron configurations would be necessary to describe highly strained or anionic species. The NPA population introduced new concept about amide bonds, i.e., the planar geometry of nitrogen atom may not come from resonance, but from the lowering of p-orbital energy by electronegative carbonyl carbon atom. The issues for hypervalent atomic charges was also addressed by various charge derivation scheme. When the charge schemes were applied to organolithium compounds, the ionic nature of boding was revealed. This comes from the fact that previous Mulliken partial atomic charges overemphasized the covalent character, wihout much justification. The other partial charge derivation schemes such as NPA(natural population analysis), IPP (Integrated Projected Population) showed that much more ionic picture. ESP potential derived charges are generally believed to be suitable to describe intermolecular interactions, therefore they are used for molecular dynamics simulations and CoMFA (comparative molecular field analysis). The charge derivation schemes using multipole polarization was mainly applied to reproduce experimental infrared spectroscopy. In some reports these schemes are also suitable for intermecular electrostatic interactions. Charges derived from electron density gradient have shown the some bonds are not straight, but actually bent. The proper choice of charge-calculation method along with suitable level of theory and basis set are briefly discussed.

• Journal of the Korean Chemical Society
• /
• v.21 no.2
• /
• pp.75-82
• /
• 1977

The isotope effect of pure liquid on vapor pressure is examined, and the vapor pressure ratios of two different isotopes are calculated. Based on the Significant Structure Theory of Liquids, the effect of molecular weight and the effect of moments of inertia are dominant in ordinary/trans-$d_2$ ethylene isotopes; the effect of hindered rotational zero-point energy is dominant in trans-$d_2$/cis-$d_2$ ethylene isotopes; and the effect of intermolecular potential difference is found in $CH_3OH/CH_3OD$ isotopes. In the isotopes of $CH_4/CD_4,\;SiH_4/SiD_4\;and\;GeH_4/GeD_4$, the weight effect decrease in the order of $CH_4/CD_4 >SiH_4/SiD_4 >GeH_4/GeD_4$.

• Journal of the Korean Chemical Society
• /
• v.29 no.6
• /
• pp.592-598
• /
• 1985

The total vibrational deexcitation rate constants $k_{v,v-1}$ of HF(v = 5-7) by HF(${\mu}$ = 0) and DF(${\mu}$ = 9-12) by DF(${\mu}$= 0) including both the vibration to vibration (V ${\to}$ V) and vibration to rotation and translation (V ${\to}$ R, T) energy transfer channels have been calculated semiclas-sically using a simplified collision model. The calculated results are in reasonably good agreement with those obtained by experimental and other theoretical studies. The rate constants increase with increasing temperature and also with increasing v. They also show that the relaxation of the highly excited HF and DF occurs predominantly via the V ${\to}$ R, T path at low temperature. The effectiveness of the V ${\to}$ V path, however, increases as the temperature is raised.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.4
• /
• pp.495-502
• /
• 2006

Intramolecular energy flow and C-$H_{methyl}$ and C-$H_{ring}$ bond dissociations in vibrationally excited toluene in the collision with HF have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited toluene upon collision is not large and it increases slowly with increasing total vibrational energy content between 20,000 and 45,000 $cm ^{-1}$. Above the energy content of 45,000 $cm ^{-1}$, however, energy loss decreases. Furthermore, in the highly excited toluene, toluene gains energy from incident HF. The temperature dependence of energy loss is negligible between 200 and 400 K. Energy transfer to or from the excited methyl C-H bond occurs in strong collisions with HF transferring relatively large amount of its translational energy (>> $k_BT$) in a single step, whereas energy transfer to the ring C-H bond occurs in a series of small steps. When the total energy content $E_T$ of toluene is sufficiently high, either C-H bond can dissociate. The C-$H_{methyl}$ dissociation probability is higher than the C-$H_{ring}$ dissociation probability. The dissociation of the ring C-H bond is not the result of the intermolecular energy flow from the direct collision between the ring C-H and HF but the intramolecular flow of energy from the methyl group to the ring C-H stretch. The C-$H_{ring}$${\cdot}{\cdot}{\cdot}$HF interaction is not important in transferring energy and in turn bond dissociation.

• Journal of the Korean Chemical Society
• /
• v.47 no.2
• /
• pp.104-108
• /
• 2003

The reaction of $[Cu(L)]Cl_2{\cdot}H_2O(L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^{1.18},0^{7.12}]docosane)$ with 2,5-pyridinedicarboxylate(pdc) led to the formation of $[Cu(L)(H_2O)](pdc){\cdot}6H_2O(1)$. The structure was characterized by X-ray crystallography and spectroscopic method. The coordination geometry around the copper atom is a distorted square-pyramid with four secondary amines of the macrocycle occupying the basal sites and a water molecule at the axial position. Intermolecular hydrogen bonds in 1 form a three-dimensional molecular network.

• Journal of Adhesion and Interface
• /
• v.6 no.4
• /
• pp.1-6
• /
• 2005

In this work, the effect of chemical treatments on surface properties of SiC was investigated in crack resistance properties of SiC/epoxy composites. The surface properties of SiC were determined by acid/base values and FT-IR measurements. Also the crack resistance properties of the composites were studied in critical strain energy release rate mode II ($G_{IIC}$) measurements. As a result, the acidically treated SiC had higher acid value than that of untreated SiC or basically treated SiC. The crack resistance properties of the composites had been improved in the specimens treated by acidic solution. These results were could be attributed to the acide-base intermolecular interaction between SiC and epoxy resin, resulting in increase of the degree of adhesion at interfaces.