• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.235-240
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• 2007

Molecular structures were optimized for the 1,3-diethoxycalix[4]crown-5-ether (2) in the various isomers and their potassium-ion complexes by using B3LYP/6-31+G(d,p)//B1LYP/6-31G(d,p) method after ab initio RHF/6-31G calculation. The cone-shaped isomer of 2 with cr-binding mode has shown the strongest binding efficiency among the six different complexes attributed to seven electrostatic interactions between the potassium cation and the oxygen atoms of crown-5-ether and ethoxy groups of the host (2). The vibrational spectra of 2 and its K+-complexes were obtained by restricted Hartree-Fock (RHF) calculations with the 6-31G basis set. The characteristic vibrational frequencies of various C-O-C stretching and bending motions are analyzed.

• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.553-557
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• 2013

The stretching vibration of OH of ice Ih is studied by Car-Parrinello molecular dynamics in regarding the effect of mixed H/D contamination while the vibrational spectrum is considered by velocity-velocity autocorrelations of the sampled ensemble. When hydrogen atoms are immersed randomly into the deuterated ice, a typical vibrational frequency of OH stretching mode is observed to be similar to that from the pure $H_2O$ ice. When focusing on the correlation of isolated neighboring OH stretching, a narrower and blue shifted peak is observed at the high frequency range as a result of the screening from the complex many body correlations by $D_2O$ environment. It is also specifically related to the symmetric intermolecular correlations between neighboring OH stretching modes. More enhanced high frequency range can be explained by the expansion of such two body correlations to collective many body correlations among all possible OH stretching modes. This contribution becomes important when it involves in chemical interactions via excitation of such vibrational states.

• Bulletin of the Korean Chemical Society
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• v.25 no.9
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• pp.1397-1402
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• 2004

The vibrational predissociation of triatomic, i.e., atom-diatom, van der Waals complexes in transient electronic excited state has been widely investigated. The predissociation rates or lifetimes are major concerns of the previous studies. Experimentally rotational state distributions of diatomic product are hardly investigated and few theoretical stuides on rotational state distributions have appeared in literature. In this work, choosing the frequently studied $I_2(B)-Ne$ complex as an example, we investigate the change of rotational state distributions of $I_2(B)-Ne$ produced from predissociation of the various initial states of $I_2(B)-Ne$. The present study on the rotational distributions indicates that rotational state distributions depend significantly on the predissociation energy and the van der Waals vibrational modes of $I_2(B)-Ne$. That is, the initial state dependency of rotational state distributions is extensively discussed.

• The Transactions of the Korean Institute of Electrical Engineers P
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• v.59 no.4
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• pp.440-443
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• 2010

This paper deals with the method of vibration measurement of a gun barrel structure using mechanical filter. When a bullet with high speed is moving within a gun barrel type structure with low bending vibration frequencies, it is difficult to measure the bending vibration signals of the structure. For example, noncontact type sensors such as displacement or velocity sensor are not appropriate for the measurement of vibrational signals because of the movement effect of the equipment frame through the moving structures or effect of the ground vibration. One of contact type sensors such as accelerometer is profitable for measurement of vibrational signals because of its wide measurement ranges. In the case of a gun barrel structure including high vibrational signals like shock waves, however, it is necessary to propose vibration measurement method filtering high frequencies. The purpose of the paper is to propose the proper vibrational measurement technique filtering high frequencies of a gun barrel type structure.

• Bulletin of the Korean Chemical Society
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• v.22 no.7
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• pp.721-726
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• 2001

The vibrational transition probability expressions for the forced Morse oscillator have been derived using the commutation relations of the anharmonic Boson operators. The formulation is based on the collinear collision model with the exponential repulsive potential in the framework of semiclassical collision dynamics. The sample calculation results for H2+ He collision system, where the anharmonicity is large, are in excellent agreement with those from an exact, numerical quantum mechanical study by Clark and Dickinson, using the reactance matrix. Our results, however, are markedly different from those of Ree, Kim and Shin's in which they approximate the commutation operator I。 as unity, the harmonic oscillator limit. We have concluded that the quantum number dependence in I。 must be retained to get accurate vibrational transition probabilities for the Morse oscillator.

• Bulletin of the Korean Chemical Society
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• v.15 no.9
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• pp.762-765
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• 1994

Picosecond time-resolved resonance Raman spectroscopy has been used to study the photochemistry of Cr(CO$)_6$ in cyclohexane following photoexcitation at 266 nm. Photodissociative loss of CO is found to occur within our pulse width of ${\leq}$5 ps by probing the 533 c$m^{-1}$ vibrational mode of ground state Cr(CO$)_6$. The subsequent dynamics after photodissociation are interpreted in terms of solvation, vibrational and electronic relaxations. The vibrational relaxation time of 100 ps and 83 ps are observed by monitoring v=O and v=l of the 381 c$m^{-1}$ transient mode, respectively. No evidence was found for solvation and electronic relaxation occurring on a time scale of ${\leq}$5 ps.

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

• Bulletin of the Korean Chemical Society
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• v.22 no.6
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• pp.605-610
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• 2001

The molecular geometries and harmonic vibrational frequencies of dibenzofuran in the ground and lowest triplet state have been calculated using the Hartree-Fock and Becke-3-Lee-Yang-Parr(B3LYP)density functional methods with the 6-31G basis set. Upon the excitation to the lowest triplet state, the molecular structure retains the planar form but distorts from a benzene-like to a quinone-like form in skeleton. Scaled vibrational frequencies for the ground and lowest triplet state obtained from the B3LYP calculation show excellent agreement with the available experimental data. A few vibrational fundamentals for both states are newly assigned based on the B3LYP results.

• Bulletin of the Korean Chemical Society
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• v.16 no.4
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• pp.341-344
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• 1995

Laser-induced fluorescence (LIF) excitation spectra were measured for fluorene (FR) cooled in pulsed supersonic expansions of He in the range 283.7-296.7 nm. Ab initio studies of FR have also been carried out for determining the electronic and vibrational structures by using the standard 3-21G basis sets. In the LIF excitation spectra of FR, highly resolved vibronic bands are observed having the band origin of 33,791 cm-1. The vibrational bands above the electronic origin were assigned on the basis of the well-characterized electronic vibrational bands reported previously and of normal modes of vibrations derived by our HF/3-21G calculations.

• Journal of the Korean Chemical Society
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• v.67 no.6
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• pp.407-414
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• 2023

The present study uses quasi-classical trajectory procedures to examine the vibrational relaxation and dissociation of the methyl and ring C-H bonds in excited methylpyrazine (MP) during collision with either N₂ or O₂. The energy-loss (-ΔE) of the excited MP is calculated as the total vibrational energy (E_T) of MP is increased in the range of 5,000 to 40,000cm^-1. The results indicate that the collision-induced vibrational relaxation of MP is not large, increasing gradually with increasing E_T between 5,000 and 30,000 cm^-1, but then decreasing with the further increase in E_T. In both N₂ and O₂ collisions, the vibrational relaxation of MP occurs mainly via the vibration-to-translation (V→T) and vibration-to-vibration (V→V) energy transfer pathways, while the vibration-to-rotation (V→R) energy transfer pathway is negligible. In both collision systems, the V→T transfer shows a similar pattern and amount of energy loss in the ET range of 5,000 to 40,000cm^-1, whereas the pattern and amount of energy transfer via the V→V pathway differs significantly between two collision systems. The collision-induced dissociation of the C-H_methyl or C-H_ring bond occurs when highly excited MP (65,000-72,000 cm^-1) interacts with the ground-state N₂ or O₂. Here, the dissociation probability is low (10^-4-10^-1), but increases exponentially with increasing vibrational excitation. This can be interpreted as the intermolecular interaction below E_T = 71,000 cm^-1. By contrast, the bond dissociation above E_T = 71,000 cm^-1 is due to the intramolecular energy flow between the excited C-H bonds. The probability of C-H_methyl dissociation is higher than that of C-H_ring dissociation.