• Bulletin of the Korean Chemical Society
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• 제20권6호
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• pp.657-662
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• 1999

The variation of Jahn-Teller(J-T) distortion imposed on various metallo- tetraphenylporphyrins(MTPPS;M=ZnⅡ,PdⅡ,PtⅡ,and RhⅢ) has been investigated by time-resolved resonance Raman spectroscopy. B1g and B2g modes of the triplet(π,π*) states for the heavy-metal porphyrins exhibit the enhancement of their intensities compared with those of 3ZnⅢTPP, while the enhancement of phenyl internal mode is reduced. These results suggest that the J-T distortion becomes manifest as the metal size increases, and consequently the porphyrin-to-phenyl ring charge transfer in the excited triplet state is inhibited.

• Current Optics and Photonics
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• 제1권5호
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• pp.544-550
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• 2017

This simulation based study reports a novel tunable, compact, room temperature terahertz (THz) transistor source, operated on the concept of charge plasma oscillation with the capability of radiating within a terahertz gap. A vertical cavity with a quasi-periodic distributed-Bragg-reflector has been attached to a THz plasma wave transistor to achieve a monochromatic coherent surface emission for single as well as multi-color operation. The resonance frequency has been tuned from 0.5 to 1.5 THz with the variable quality factor of the optical cavity from 5 to 290 and slope efficiency maximized to 11. The proposed surface emitting terahertz transistor is able to satisfy the demand for compact solid state terahertz sources in the field of teratronics. The proposed device can be integrated with Si CMOS technology and has opened the way towards the development of silicon photonics.

• Journal of Korean Vacuum Science & Technology
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• 제2권1호
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• pp.13-19
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• 1998

We have calculated the electronic structure of impurity atoms in metal host by using the tight binding model in the recursion method. For a self-consistent calculation, we assumed that the effect of impurity introduction was localized only at the impurity site and its neighbours. We calculated the Madelung term by limiting the contribution to Vm of the charge perturbations to the first shell around the impurity with Evjen technique. The calculated local density of states and charge transfer values have been compared with the experimental values for a single impurity in metal host. We fund that d-reso-nance state came from the repulsive interaction between impurity d-state and host band, and the position of d-resonance state depended on the difference of valence electrons between the host and the impurity. the results also showed that the charge transfer value between an impurity and host metal was comparable to the ionicity difference between them.

• 대한화학회지
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• 제16권1호
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• pp.33-39
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• 1972

The stabilization energies by interconjugations at the transition states in various Diels-Alder reactions were calculated. It has been found that the stabilization energies are inversely proportional to resonance energies of isolated molecules of polyene and heterocyclic system before reactions. It has been noted that the resonance energies of dienes are smaller than those of dienophiles in two different molecules. Therefore, the possibility of charge-transfer from dienes to dienophiles is hinted.

• Current Optics and Photonics
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• 제2권4호
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• pp.378-382
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• 2018

In most previous investigations of plasmonic and metamaterial applications, the metallic film has been regarded as a perfect electrical conductor. Here we demonstrate the resonance characteristics of THz metamaterials fabricated from metal film that has a finite dielectric constant, using finite-difference time-domain simulations. We found strong redshift and spectral broadening of the resonance as we decrease the metal's plasma frequency in the Drude free-electron model. The frequency shift can be attributed to the effective thinning of the metal film, originating from the increase in penetration depth as the plasma frequency decreases. On the contrary, only peak broadening occurs with an increase in the scattering rate. The metal-thickness dependence confirms that the redshift and spectral broadening occur when the effective metal thickness drops below the skin-depth limit. The electromagnetic field distribution illustrates the reduced field enhancement and reduced funneling effects near the gap area in the case of low plasma frequency, which is associated with reduced charge density in the metal film.

• Bulletin of the Korean Chemical Society
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• 제18권6호
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• pp.657-662
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• 1997

Gas-phase phenyl group migration within the protonated ketones has been studied MO theoretically using the AM1 method. The initial state structure shows relatively strong resonance delocalization of positive charge into the nonmigrating (Y) ring, while the ring migration (Z-ring) is nearly complete in the transition state. These results are reflected in the large $p^+_Z$ (<0) and $p^+_$Y (>0) values and in the predominant contribution of resonance (r) over inductive (field, f) effect, r/f ranging from 1.3 ($p^+_r$) to 1.5 ($p^+_z$). The cross-interaction constant $p_{YZ}$ is vanishingly small ($p_{YZ}$=0.03) which is in contrast to the larger magnitudes for benzilic ($p_{YZ}$=-0.48) and azibenzil ($p_{YZ}$=-0.53) rearrangement processes. The relationship found between the extent of resonance contribution in the initial state and the magnitude of $p_{YZ}$ provides strong support for the proportionality between the magnitude of $p_{YZ}$ and the change in the intensity of interaction, ${\Delta}I^{\cdot}_{YZ}$, in the activation process.

• 대한화학회지
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• 제30권2호
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• pp.172-180
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• 1986

치환-벤조산, -베젠 및 -나프탈렌의 세 계열에 대해 LCAO MO법으로 Hammett치환기 상수를 해석하였다. Hammett ${\sigma}$값은 이론적으로 유도효과와 공명효과의 독립적인 기여의 합으로 취급됨을 알았다. 즉, 유도효과를 정적유도효과(static inductive effect, Is)와 동적유도효과 (dynamic inductive effect, Id)로 나누어 각각 net charge 및 근사자기편극률 지수로 취하고 공명효과로서 치환 분자와 비치환분자의 HOMO에너지 차$({\Delta}E^{HOMO})$로 취하였으며 계산결과 Hammett ${\sigma}$값은 정적유도효과, 동적유도효과 및 ${\Delta}E^{HOMO}$의 합에 의존됨을 알았다.

• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.188-196
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• 2013

We have investigated the effects of formalin on the assembly of colloidal gold nanoparticles (AuNPs) prepared by laser ablation of a solid gold target in deionized water. Upon addition of formalin, the surface plasmon resonance (SPR) band at 519 nm for pure AuNPs decreases and shifts to red while a new broad SPR band appears at ~700 nm. The red-shift is prominent with increase in the incubation time. The average size of the initial AuNPs is around 12 nm but it increases to 23 nm after addition of formalin. It turns out that formalin acts as a cationic surfactant for AuNPs with negative surface charge in the colloidal solutions. Furthermore, through analysis of the Raman spectrum of formalin and the density functional theory calculations, we confirm that methanediol is the main species in formalin which is in charge of the aggregation of AuNPs.

• Bulletin of the Korean Chemical Society
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• 제30권9호
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• pp.2061-2065
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• 2009

Two simple algorithm modifications are made to the THRASH data retrieval program with the aim of improving analysis speed for complex Fourier transform ion cyclotron resonance (FTICR) mass spectra. Instead of calculating the least-squares fit for every charge state in the backup charge state determination algorithm, only some charge states are pre-selected based on the plausibility values obtained from the FT/Patterson analysis. Second, a modification is made to skip figure-of-merit (FOM) calculations in the central m/z region between two neighboring peaks in isotopic cluster distributions, in which signal intensities are negligible. These combined modifications result in a significant improvement in the analysis speed, which reduces analysis time as much as 50% for ubiquitin (8.6 kDa, 76 amino acids) FTICR MS and MS/MS spectra at the reliability (RL) value = 0.90 and five pre-selected charge states with minimal decreases in data analysis quality (Table 3).

• Bulletin of the Korean Chemical Society
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• 제26권5호
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• pp.740-746
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• 2005

In this article, we report the tandem mass spectrometry investigations for the electron capture efficiencies of the protons belonging to the different locations (generations) in a poly(propylene imine) dendrimer with three layers of a repeat unit (named as the third generation dendrimer). The employed tandem mass spectrometry methods include SORI-CAD (sustained off-resonance irradiation collisional activation dissociation) and ECD(electron capture dissociation) mass spectrometry. We obtained SORI-CAD spectra for the dendrimer ions in the different charge states, ranging from 2+ to 4+. The analysis of fragmentation sites provides the information as to where the protons are distributed among various generations of the dendrimer. Based upon this, a new strategy to study the electron capture efficiencies of the protons is utilized to examine a new type of triplycharged ions by SORI-CAD, i.e., the 3+ ions generated from the charge reduction of the native 4+ ions by ECD: (M+4H)$^{4+}\;+\;e^-\;{\rightarrow}$ (M+4H)$^{3+\bullet}$ ${\rightarrow}\;({H^{\bullet}}_{ejected}$) + (M+3H)$^{3+}\;\rightarrow$ CAD. Interestingly, comparison of these four SORICAD spectra indicates that the proton distribution in the charge-reduced 3+ ions is very close to that in the native 4+ ions. It further suggests that in this synthetic polymer ($\sim$1.7 kDa) with an artificial architecture, the electron capture efficiencies of the protons are actually insensitive to where they are located in the molecule. This is somewhat contradictory to common expectations that the protons in the inner generations may not be well exposed to the incoming electron irradiation as much as the outer ones are, thus may be less efficient for electron capture. This finding may carry some implications for the case of medium sized peptide ions with similar masses, which are known to show no obvious site-specific fragmentations in ECD MS.