• Bulletin of the Korean Chemical Society
• /
• v.34 no.1
• /
• pp.179-187
• /
• 2013

We describe newly developed software named KPACK for relativistic electronic structure computation of molecules containing heavy elements that enables the two-component ab initio calculations in Kramers restricted and unrestricted formalisms in the framework of the relativistic effective core potential (RECP). The spin-orbit coupling as relativistic effect enters into the calculation at the Hartree-Fock (HF) stage and hence, is treated in a variational manner to generate two-component molecular spinors as one-electron wavefunctions for use in the correlated methods. As correlated methods, KPACK currently provides the two-component second-order M${\o}$ller-Plesset perturbation theory (MP2), configuration interaction (CI) and complete-active-space self-consistent field (CASSCF) methods. Test calculations were performed for the ground states of group-14 elements, for which the spin-orbit coupling greatly influences the determination of term symbols. A categorization of three procedures is suggested for the two-component methods on the basis of spin-orbit coupling manifested in the HF level.

• Bulletin of the Korean Chemical Society
• /
• v.8 no.2
• /
• pp.122-126
• /
• 1987

Oribtal energies for AuH and AgH are calculated by an all-electron relativistic self-consistent-field method using Slater type basis functions. Major relativistic effects for AgH are spin-orbit splittings and those for AuH are large shifts in orbital energies in addition to spin-orbit splittings. Relativistic effects on orbital energies in AgH and AuH imply that changes in correlation energies for relativistic calculations of AuH will be significantly larger than those of AgH, providing partial explanation for the large discrepencies in equilibrium bond length and the dissociation energy between experiments and theoretical estimates for AuH. Large relativistic effects on orbital energies indicate that relativistic contributions should be included for the correct interpretation of ionization potentials for these molecules. Relativistic effects are also evident in dipole moments for these molecules.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.11
• /
• pp.1186-1191
• /
• 1997

Solvolyses of methanesulfonyl chloride (CH3SO2Cl) in water and methanol have been studied theoretically using ab initio self-consistent reaction field (SCRF) molecular orbital method. All stationary structures including transition state on the potential energy surface in solution have been found and compared with the gas phase structures. The overall reaction occurs via a concerted SN2 mechanism with a non-cyclic trigonal bipyramidal transition state, and the activation barrier is lowered significantly in solution. The transition state for the hydrolysis reaction is looser than that for the methanolysis reaction, and this is in accord with the experimental findings that an SN2 type mechanism, which is shifted toward an SN1 process or an SAN process in the hydrolysis and alcoholysis reaction, respectively, takes place. The catalytic role of additional solvent molecules appears to be a purely general-base catalysis based on the linear transition structures. Experimental barrier can be estimated by taking into account the desolvation energy of nucleophile in the reaction of methanesulfonyl chloride with bulk solvent cluster as a nucleophile.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.5
• /
• pp.539-544
• /
• 1998

A new theoretical method, named the SCF-DWB-IOS approximation, is suggested to investigate the vibrational predissociation of triatomic van der Waals complexes. The meta stable vibrational excited states are described with SCF (self-consistent-field) approximation and the fragmented diatomic continuum states are determined by using IOS (infinite order sudden) approximation. The dissociation process itself is studied by using DWB (distorted wave Born) approximation. As a test case, the predissociation rates, rotational state distributions of products, and the lifetimes of vibrationally excited states of $Ne-I_2$ are all computed which are in reasonable agreements with other theoretical and/or experimental results. The suggested SCF-DWB-IOS approximation scheme is found to be a very simple but efficient theoretical tool to investigate the vibrational predissociation dynamics of small van der Waals complexes.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.20 no.1
• /
• pp.14-18
• /
• 2007

The electric property in the $GaAs-Al_{x}Ga_{1-x}$ quantum well with the Si ${\delta}-doping$ layer in a non-central position is studied through the effect of the electric field intensity on the electron distribution. The finite difference method is used for the calculation of the subband energy level and its wavefunction. In order to account for the change of the potential energy due to the charged particles, the self consistent method is employed. As the Si ${\delta}-doping$ layer becomes closer to the heterojunction interface, the electrons less affected by Coulomb scattering are greatly increased under the external electric field. Therefore, the high speed device is suggested due to the fact that the high mobility electrons can be increased by positioning the ${\delta}-doping$ layer in the quantum well and by applying the electric field intensity.

• Journal of KIISE:Software and Applications
• /
• v.33 no.5
• /
• pp.499-507
• /
• 2006

Recently human gait has been considered as a useful biometric supporting high performance human identification systems. This paper proposes a view-based pedestrian identification method using the dynamic silhouettes of a human body modeled with the Hidden Markov Model(HMM). Two types of gait models have been developed both with an endless cycle architecture: one is a discrete HMM method using a self-organizing map-based VQ codebook and the other is a continuous HMM method using feature vectors transformed into a PCA space. Experimental results showed a consistent performance trend over a range of model parameters and the recognition rate up to 88.1%. Compared with other methods, the proposed models and techniques are believed to have a sufficient potential for a successful application to gait recognition.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.1397-1402
• /
• 2014

The complete active space self-consist field method followed by the internally contracted multireference configuration interaction method has been used to compute the potential energy curves of $X^2\prod_g$, $a^4\prod_u$, $A^2\prod_u$, $b^4\sum_{g}^{-}$, and $B^2\sum_{g}^{-}$ states of $S{_2}^+$ cation with large correlation-consistent basis sets. Utilizing the potential energy curves computed with different basis sets, the spectroscopic parameters of these states were evaluated. Finally, the transition dipole moment and the Franck-Condon factors of the transition from $A^2\prod_u$ to $X^2\prod_g$ were evaluated. The radiative lifetime of $A^2\prod_u$ is calculated to be 887 ns, which is in good agreement with experimental value of $805{\pm}10$ ns.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.2
• /
• pp.245-252
• /
• 2002

The computationally simple quantum mechanical method (VSCF-DWB-IOS) has been applied to studying the Ar-$CO_2$ vibrational predissociation phenomenon. The new methodology utilizes the vibrational self-consistent field method to determine the vibrational structure of the van der Waals complex, the distorted-wave Born approximation for dissociating process, and the infinite-order sudden approximation for the continuum dissociating product of $CO_2$. The dissociation due to the coupling of the symmetric stretching vibrational motion of $CO_2$ with the motion of the Ar van der Waals mode has been extensively investigated. The lifetimes of transient excited vibrational states, linewidths of absorption peak, and the rotational state distributions of the product, $CO_2$ have been computed. It has been found that the lifetime of the Ar-$CO_2$ in excited vibrational state is very long compared with that of triatomic van der Waals complexes and the product $CO_2$ carries a major portion of dissociation energy as a rotational energy.

• Journal of the Korean Vacuum Society
• /
• v.13 no.3
• /
• pp.132-138
• /
• 2004

We used the self-consistent one-dimensional model applied to FCT algorithm and FEM method in a wire-cylinder type reactor to study the characteristics of corona discharge plasma in air at the atmospheric pressure. At the pulsed do voltage and do voltage, we studied the changes of the characteristic of plasma by computing electron density profile according to the changes of voltage and the size of reactor. The changes of active radius from this result are compared with the data of Peek's. The numerical simulation results for a corona discharge plasma explain the physical mechanism of the discharge process and could be used to obtain the optimized parameters for designing the plasma reactor for pollution abatement.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.2
• /
• pp.363-371
• /
• 2008

As a computational method for the discovery of the effective agonists for PPARd, we address the usefulness of molecular dynamics free energy (MDFE) simulation with explicit solvent in terms of the accuracy and the computing cost. For this purpose, we establish an efficient computational protocol of thermodynamic integration (TI) that is superior to free energy perturbation (FEP) method in parallel computing environment. Using this protocol, the relative binding affinities of GW501516 and its derivatives for PPARd are calculated. The accuracy of our protocol was evaluated in two steps. First, we devise a thermodynamic cycle to calculate the absolute and relative hydration free energies of test molecules. This allows a self-consistent check for the accuracy of the calculation protocol. Second, the calculated relative binding affinities of the selected ligands are compared with experimental IC50 values. The average deviation of the calculated binding free energies from the experimental results amounts at the most to 1 kcal/mol. The computational efficiency of current protocol is also assessed by comparing its execution times with those of the sequential version of the TI protocol. The results show that the calculation can be accelerated by 4 times when compared to the sequential run. Based on the calculations with the parallel computational protocol, a new potential agonist of GW501516 derivative is proposed.