• Bulletin of the Korean Chemical Society
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• v.10 no.1
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• pp.60-66
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• 1989

Semiempirical computations using the AM1 and MNDO methods were carried out in order to elucidate allowed mechanisms for 1,3-group(X) rearrangement processes with X = $BH_2$, $CH_3$, CN, F, $NH_2$, OH, Cl and SH. The reactivity of the group migration was largely controlled by the steric effect in the 4-membered ring transition state, an antarafacial process having a greater energy barrier due to a greater steric repulsion. For the groups with lone pair electrons, the participation of the lone pair orbital is found to ease the steric effect by enabling the FMO interation with highly polarizable, high lying, lone pair electrons at relatively distant range; the involvement of lone pairs in the transition state causes an alteration of the symmetry selection rule to that of a 6-electron system with an allowed 1,3-suprafacial migration in contrast to an allowed 1,3-antarafacial migration for a 4-electron system. Various stereoelectronic aspects were analysed in some detail.

• Journal of the Korean Chemical Society
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• v.53 no.3
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• pp.266-271
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• 2009

In the recently synthesized rare earth transition metal carbide $La_7O_{s4}C_9$ one finds one-dimensional organometallic $[O_{s4}C_9]^{21-}$ polymers embedded in a $La^{3+}$ ionic matrix. The electronic structure of the polymeric $[O_{s4}C_9]^{21-}$ chain was investigated by density of states (DOS) and crystal orbital overlap population (COOP), using the extended Huckel algorithm. A fragment molecular orbital analysis is used to study the bonding characteristics of the $C_2$ units in $La_7O_{s4}C_9$ containing $C_2$ units and single C atoms as well. The title compound contains partially filled Os and carbon bands leading to metallic conductivity. As the observed distances already indicated, the calculations show extensive Os-C interactions. The C-C bond distance in the diatomic $C_2$ units ($d_{C-C}$=131 pm) in the solid is significantly increased relative to $${C_2}^{2-}$$ or acetylene, because antibonding $1{\pi}_g$ orbitals are partially filled by the Os-$C_2(1\;{\pi}_g)$ bonding contribution found at and below the Fermi level.

• Journal of the Korean Chemical Society
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• v.26 no.1
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• pp.7-17
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• 1982

In order to predict substituent and Lewis acid effects on the regiospecificity of the Diels-Alder reaction, and to investigate the competition for the complexation of Lewis acid between diene and dienophile, frontier orbital theory has been applied to thermal and catalyzed Diels-Alder reaction by means of CNDO/2 MO method. It has been found that: (1) Lewis acid coordinated preferentially with diene rather than dienophile when carbonyl oxygen of acetoxy substituted diene had larger negative atomic charges than that of dienophile. (2) Most of the reaction were neutral electron demand type, and hence 4-C, 2-C and quantitative secondary orbital interacion methods were generally in good accord with experiments. (3) Sulfur activated the adjacent terminal carbon atom greatly to increase diene LUMO-dienophile HOMO interaction through vacant-d-orbital participation, and played an important role in controlling regioselectivity of neutral electron demand reaction type.

• The Journal of Korean Institute of Communications and Information Sciences
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• v.34 no.1C
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• pp.37-47
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• 2009

When H.264 encoded video streams are transmitted over wireless network, packet loss is unavoidable. Responding on this environment, we propose methods to recover missed motion vector in the decoder: At first, A candidate vector set for missing macroblock is estimated from high correlation coefficient of neighboring motion vectors and missing block vectors the algorithm clusters candidate vectors through distances amongst motion vectors of neighboring blocks. Then the optimal candidate vector is determined by the median value of the clustered motion vector set. In next stage, from the candidate vector set, the final candidate vector of missing block is determined it has minimum distortion value considering directions of neighboring pixels' boundary. Test results showed that the proposed algorithm decreases the candidate motion vectors $23{\sim}61%$ and reduces $3{\sim}4sec$ on average processing(decoding) time comparing the existing H.264 codec. The PSNR, in terms of visual quality is similar to existing methods.

• The Journal of the Korea Contents Association
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• v.8 no.5
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• pp.29-37
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• 2008

To transmit video bit stream over low bandwidth such as wireless channel, high compression algorithm like H.264 codec is exploited. In transmitting high compressed video bit-stream over low bandwidth, packet loss causes severe degradation in image quality. In this paper, a new algorithm for recovery of missing or erroneous motion vector is proposed. Considering that the missing or erroneous motion vectors in blocks are closely correlated with those of neighboring blocks. Motion vector of neighboring blocks are clustered according to average linkage algorithm clustering and a representative value for each cluster is determined to obtain the candidate motion vector sets. As a result, simulation results show that the proposed method dramatically improves processing time compared to existing H.264/AVC. Also the proposed method is similar to existing H.264/AVC in terms of visual quality.