• Bulletin of the Korean Chemical Society
• /
• 제7권3호
• /
• pp.170-178
• /
• 1986

The NMR chemical shift arising from 4d electron angular momentum and 4d electron angular momentum and 4d electron spin dipolar-nuclear spin angular momentum interactions for a $4d^1$ system in a strong crystal field environment of trigonal symmetry, when the threefold axis is chosen to be the axis of quantization axis, has been examined. A general expression using the nonmultipole expansion method (exact method) is derived for the NMR chemical shift. From this expression all the multipolar terms are determined. We observe that along the (100), (010), (110), and (111) axes the NMR chemical shifts are positive while along the (001) axis, it is negative. We observe that the dipolar term (1/R3) is the dominant contribution to the NMR chemical shift except for along the (111) axis. A comparison of the multipolar terms with the exact values shows also that the multipolar results are exactly in agreement with the exact values around $R{\geqslant}0.2$ nm. The temperature dependence analysis on the NMR chemical shifts may imply that along the (111) axis the contribution to the NMR chemical shift is dominantly pseudo contact interaction. Separation of the contributions of the Fermi and the pseudo contact interactions would correctly imply that the dipolar interaction is the dominant contribution to the NMR chemical shifts along the (100), (010), (001), and (110) axes, but along the (111) axis the Fermi contact interaction is incorrectly the dominant contribution to the NMR chemical shift.

• Korea-Australia Rheology Journal
• /
• 제19권3호
• /
• pp.147-156
• /
• 2007

The orientation and deformation of polymer chains in a confined channel flow has been investigated. The polymer chain was modeled as a Finitely Extensible Nonlinear Elastic (FENE) dumbbell. The Brownian configuration field method was extended to take the interaction between the flow and local chain dynamics into account. Drag and Brownian forces were treated as anisotropic in order to reflect the influence of the wall in the confined flow. Both Poiseuille flow and 4 : 1 contraction flow were considered. Of particular interest was molecular tumbling of polymer chains near the wall. It was strongly influenced by anisotropic drag and high shear close to the wall. We discussed the mechanism of this particular behavior in terms of the governing forces. The dumbbell configuration was determined not only by the wall interaction but also by the flow type of the geometric origin. The effect of extensional flow on dumbbell configuration was also discussed by comparing with the Poiseuille flow.

• Korea-Australia Rheology Journal
• /
• 제21권2호
• /
• pp.91-102
• /
• 2009

This paper describes an extension of viscoelastic Group Interaction Modelling (GIM) to predict the relaxation response of linear, branched and cross-linked structures. This model is incorporated into a Monte Carlo percolation grid simulation used to generate the topological structure during the isothermal cure of a gel, so enabling the chemorheological response to be predicted at any point during the cure. The model results are compared to experimental data for an epoxy-amine systems and good agreement is observed. The viscoelastic model predicts the same exponent power-law behaviour of the loss and storage moduli as a function of frequency and predicts the cross-over in the loss tangent at the percolation condition for gelation. The model also predicts the peak in the loss tangent which occurs when the glass transition temperature surpasses the isothermal cure temperature and the system vitrifies.

• Korea-Australia Rheology Journal
• /
• 제14권4호
• /
• pp.203-207
• /
• 2002

Particle-particle interaction is of great importance in the study of suspension rheology. In this research we have investigated the hydrodynamic interaction between two identical cylinders in viscoelastic fluids numerically as a model problem for the study of viscoelastic suspension. We confine two neutrally buoyant cylinders between two parallel plates and impose a shear flow. We determine the migration velocity of two cylinders. The result shows that cylinders move toward or away from each other depending upon the initial distance between them and that there is an equilibrium distance between two cylinders in viscoelastic fluids regardless of the initial distance. In the case of Newtonian fluid, there is no relative movement as expected. The results partly explain the chaining phenomena of spherical particles in shear flows of viscoelastic fluids.

• Bulletin of the Korean Chemical Society
• /
• 제32권12호
• /
• pp.4195-4198
• /
• 2011

Intramolecular ${\pi}-{\pi}$ and ${\sigma}-{\pi}$ interactions are omnipresent for numerous energetic and structural phenomena in nature, and the exact description of these nonbonding interactions plays an important role in the accurate prediction of the three-dimensional structures for numerous interesting molecular systems such as protein folding and polymer shaping. We have selected two prototype molecular systems for benchmarking calculations of intramolecular ${\pi}-{\pi}$ and ${\sigma}-{\pi}$ interactions. Accurately describing conformational energy of such systems requires highly elaborate but very expensive ab initio methods such as coupled cluster singles, doubles, and (triples) (CCSD(T)). Our calculations reveal a double hybrid density functional incorporating dispersion correction (B2PLYP-D) that agrees excellently with the CCSD(T) results, indicating that B2PLYP-D can serve as a practical method of choice.

• Bulletin of the Korean Chemical Society
• /
• 제2권4호
• /
• pp.132-138
• /
• 1981

Ab initio molecular orbital calculations have been performed in an effort to determine which types of chemical interactions play essential roles for the system, , $H_2O+CH_2SH^+$, and $H_2O+ CH_2S$. The most important contribution to the interaction energy in controlling reaction path is the exchange repulsion energy, EX, which is largely responsible for the shape of the total interaction energy curve. In the ion-molecule reaction, prior protonation of thioformaldehyde or prior deprotonation of water leads to formation of the corresponding ionic adducts ($H_2O+CH_2SH$ and $HOCH_2S^-$), with no barrier to reaction, simulating specific acid and base catalysis, respectively, as in the case of formaldehyde. Otherwise, approach of water to thioformaldehyde gives rise to a completely repulsive interaction.

• 대한화학회지
• /
• 제29권1호
• /
• pp.23-30
• /
• 1985

${\pi}^{\ast}$-${\pi}^{\ast}$ 궤도간 상호작용에 관한 섭동식을 유도하였다. 섭동식으로부터 예측되는 ${\pi}$-${\pi}$와 ${\pi}^{\ast}$-${\pi}^{\ast}$ 상호작용간의 중요한 두가지 차이점은 : (ⅰ)에너지분리정도가 ${\pi}$-${\pi}$ 상호작용의 경우보다 ${\pi}^{\ast}$-${\pi}^{\ast}$의 경우가 더 컸으며, ( ii ) 상호작용에 의한 에너지 변화량은 ${\pi}$-${\pi}$ 상호작용의 경우보다 ${\pi}^{\ast}$-${\pi}^{\ast}$의 경우가 더 불안정화 되었다. 이러한 예측들은 실험결과들과 MO이론적 계산에 의하여 잘 밝혀졌다. 한편 STO-3G 및 INDO-LCBO 계산방법은 ${\pi}^{\ast}$-${\pi}^{\ast}$ 상호작용을 과소평가하고 있음을 알았으며 MO이론적 계산을 이용하여 이러한 ${\pi}^{\ast}$-${\pi}^{\ast}$상호작용을 적절히 표현하는 데는 split valence 기초함수를 사용하여야 함을 밝혔다.

• Bulletin of the Korean Chemical Society
• /
• 제25권6호
• /
• pp.924-926
• /
• 2004

• Korea-Australia Rheology Journal
• /
• 제19권4호
• /
• pp.233-242
• /
• 2007

We performed a numerical investigation to find out the optimal choice of the spatial discretization in the distributed-Lagrangian-multiplier/fictitious-domain (DLM/FD) method for the solid/fluid interaction problem. The elastic solid bar attached on the bottom in a pressure-driven channel flow of a Newtonian fluid was selected as a model problem. Our formulation is based on the scheme of Yu (2005) for the interaction between flexible bodies and fluid. A fixed regular rectangular discretization was applied for the description of solid and fluid domain by using the fictitious domain concept. The hydrodynamic interaction between solid and fluid was treated implicitly by the distributed Lagrangian multiplier method. Considering a simplified problem of the Stokes flow and the linearized elasticity, two numerical factors were investigated to clarify their effects and to find the optimum condition: the distribution of Lagrangian multipliers and the solid/fluid interfacial condition. The robustness of this method was verified through the mesh convergence and a pseudo-time step test. We found that the fluid stress in a fictitious solid domain can be neglected and that the Lagrangian multipliers are better to be applied on the entire solid domain. These results will be used to extend our study to systems of elastic particle in the Stokes flow, and of particles in the viscoelastic fluid.

• Bulletin of the Korean Chemical Society
• /
• 제18권2호
• /
• pp.139-141
• /
• 1997