• Mass Spectrometry Letters
• /
• v.13 no.3
• /
• pp.49-57
• /
• 2022

During electrospray ionization mass spectrometry (ESI-MS) analysis of proteins, the addition of supercharging agents allows for adjusting the maximal charge state, affecting the charge state distribution, and increases the number of ions reaching the detector thus, improving signal detection. We postulate that in di-substituted arene isomers, molecules with higher polarizability values should generate greater interactions and hence elicit higher signal intensities. Polarizability is an electronic parameter which has been demonstrated to predict many chemical interactions. Many properties can be predicted based on charge polarization. Molecular polarizability is a vital descriptor for explaining intermolecular interactions. We employed DFT (density functional/Hartree-Fock hybrid model, B3LYP)-derived descriptors and computed molecular polarizability for ten disubstituted arene reagents, each set made up of three (ortho, meta, para) isomers, with reported use as supercharging reagents during ESI experiments. The atomic electronic inputs were ionization potential (IP), electron affinity (EA), electronegativity (𝛘), hardness (η), chemical potential (µ), and dipole moment (D). We determined that the para isomers showed the highest polarizability values in nine of the ten sets. There was no difference between the ortho and meta isomers. Polarizability also increased with increasing complexity of the substituents on the benzene ring. Polarizability correlated positively with IP, EA, 𝛘, η, and D but correlated negatively with chemical potential. This DFT study predicts that the para isomers of di-substituted arene isomers should elicit the strongest ESI responses. An experimental comparison of the three isomers, especially of larger supercharging molecules, could be carried out to establish this premise.

• Journal of electromagnetic engineering and science
• /
• v.1 no.2
• /
• pp.173-175
• /
• 2001

A polarizability fur a circular aperture near a conducting plane is derived. The Mantel-transform and mode-matching is used to obtain a simple series solution. The presented series solution is fast convergent so that it is very efficient fur numerical computations.

• Journal of the Korean Chemical Society
• /
• v.22 no.2
• /
• pp.62-66
• /
• 1978

The polarizability tensor components for $NH_3,\;BH_3,\;HCN,\;C_2H_4,\;PO,\;PO^-$ and CO molecules are calculated by the variation method. The parallel components of the polarizability are closer to the experimental values than those of CNDO/2, MINDO/1 and MINDO/2, but the perpendicuar components of the polarizability are not closer to the experimental values than those of the other methods.

• Bulletin of the Korean Chemical Society
• /
• v.7 no.3
• /
• pp.183-185
• /
• 1986

Self-atom polarizability were calculated for 17 polycyclic aromatic hydrocarbons and their metabolites by LCAO-MO method and examined the relation with the carcinogenicity. It has been found that ${\pi}_{1.2.4}$, the sum of self-atom polarizability of 1, 2 and 4 positions forming trans-butadiene frame in a compound, agree quite well with the observed carcinogenic activity, and also, ${\pi}_{1.2.4}$ value increase with the metabolic activiting in agreement with the experimental facts that parent carcinogens activated with metabolism. Accordingly, we suggest that the 1, 2 and 4 positions in the carcinogenic compounds play the most important role in the process of chemical carcinogenesis, and also self-atom polarizability, as one of theoretical reactivity indices, is to be used as a measure of carcinogenic activity.

• The Journal of Korean Institute of Electromagnetic Engineering and Science
• /
• v.29 no.8
• /
• pp.594-598
• /
• 2018

The tangential electric polarizability of a electrically small square patch, which is commonly used in metasurfaces, is calculated using electric potential continuity. Since the potential at the patch surface is not uniform due to the equivalent electric dipole located at the center, there is a problem in that the polarizability is not uniquely defined. To obtain equivalent polarizability, the meshes in the analysis area are divided on the patch surface, and the equivalent polarizability is calculated by averaging the polarizabilities obtained at each point. The results of the proposed method, third-power series approximation, and experimental equations are compared and verified. Finally, the magnitude and phase of the reflection coefficient of patch metasurface calculated by generalized sheet transition conditions(GSTCs) are in good agreement with the HFSS simulation results.

• Proceeding of EDISON Challenge
• /
• 2015.03a
• /
• pp.117-123
• /
• 2015

본 연구에서는 DFT를 이용하여 Nucleophilicity와 Basicity의 연관성에 대한 계산화학적 분석을 수행하였다. Basicity는 선정된 모델 분자의 protonation 반응에서 생성물과 반응물의 enthalpy 변화량인 양성자 친화도(Proton affinity, PA) 값을 구하여 분석하였다. 계산한 결과는 실험을 통해 얻은 PA 결과와 경향성이 거의 일치함을 확인하였다. Nucleophilicity는 모델 분자들과 $CH_3Br$ (electrophile)의 $SN_2$반응에서 gibbs free energy of activation(${\Delta}G^{\ddag}$) 값으로 그 경향성을 분석하였다. 또한 용매의 종류를 다르게 하여 용매에 따른 ${\Delta}G^{\ddag}$ 값의 경향성도 확인하였다. 각 용매에 따라 구한 ${\Delta}G^{\ddag}$와 PA의 상관관계를 비교하였으나, 큰 연관성은 보이지 않았다. 이에 ${\Delta}G^{\ddag}$와 PA의 상관관계를 보여줄 수 있는 parameter를 찾기 위하여 각 모델 분자의 Electronegativity와 Polarizability를 계산하여 연관성을 비교해보았다. Polarizability를 적용했을 때 Nucleophilicity와 Basicity사이의 연관성을 나타낼 수 없었던 반면, Electronegativity를 적용하여 Basicity와 Nucleophilicity의 연관성 보일 수 있음을 이론적으로 규명하였다.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.7
• /
• pp.585-589
• /
• 1994

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of S-p-nitrophenyl thiobenzoate with various anionic nucleophiles including 6 ${\alpha}$-effect nucleophiles. A good Bronsted correlation has been observed for the reactions with 7 aryloxides. However, p-chlorothiophenoxide and hydroxide ions exhibit significantly positive and negative deviations, respectively, from the Bronsted plot. The deviations are attributed to the effect of polarizability and solvation rather than a change in the reaction mechanism. The ${\alpha}$-effect nuceophiles except highly basic ones demonstrate remarkably enhanced nucleophilicity. The effects of solvation and/or polarizability are proposed to be important for the cause of the ${\alpha}$-effect.

• Journal of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.469-479
• /
• 1991

According to the recent paper by B. Fricke (J. Chem. Phys. 84, 862 (1986)), it is reported that the atomic polarizability (${\alpha}$) correlates very strongly with the first ionization potential (IP) within the groups of elements. In our study, we obtained very significant correlations between $ln\alpha$ and IP as well as lnIP by employing the least squares method. In examining the correlations of various atomic electronegativities with their first ionization potentials and the atomic polarizability within the groups of elements, good correlation coefficients are obtained except for groups 3a and 4a. Within the periods of elements, good correlation coefficients are obtained with no exception. This allows a very good prediction of various atomic polarizabilities undetermined.

• The Journal of Korean Institute of Electromagnetic Engineering and Science
• /
• v.23 no.5
• /
• pp.652-659
• /
• 2012

Shielding effectiveness(SE) of metallic rectangular enclosure with rectangular slit apertures at horizontal polarization (HP) and vertical polarization(VP) is investigated. The magnetic polarizability of the rectangular slit apertures and the resonance modes of the metallic rectangular enclosure are analyzed theoretically. The simulation results based on these theoretical analyses are compared with the measured ones. The dependence of the shielding effectiveness on the location of the calculation probe inside the enclosure is also investigated.

• Journal of the Korean Chemical Society
• /
• v.22 no.1
• /
• pp.52-53
• /
• 1978