• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.385-388
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• 1992

The transition probabilities for the thermal intramolecular electron transfer and the optical intervalence transfer band for a symmetric mixed-valence Cu(I)-Cu(II) compound were used to extract the PKS parameters $\varepsilon$ = -1.15, ${\lambda}$ = 2.839, and ${\nu}g$- = 923 $cm^{-1}$. These parameters determine the potential energy surfaces and vibronic energy levels. Three pairs of vibrational levels are below the top of the energy barrier in the lower potential surface. The contribution of each vibrational state to the intramolecular electron transfer was calculated. It is shown that the three pairs of vibrational states below the top of the barrier are responsible for most of the electron transfer at 261-306 K. So the intramolecular electron transfer in this system is a tunneling process. The transition probability exhibits the usual high-temperature Arrhenius behavior, but at lower temperature falls off to a temperature-independent value as tunneling from the lowest levels becomes the limiting process.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1561-1565
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• 2012

The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the $NH_2$ group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [$NH_3{^+}-CHCH_3-COO{\bullet}$], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.751-754
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• 2006

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2343-2353
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• 2007

We report the application of time-dependent density functional theory (TDDFT) to the calculation of potential energy profile relevant to the excited state intramolecular proton transfer (ESIPT) processes in title molecules. The TDDFT single point energy calculations along the reaction path have been performed using the CIS optimized structure in the excited state. In addition to the Stokes shifts, the transition energies including absorption, fluorescence, and 0-0 transition are estimated from the TDDFT potential energy profiles along the proton transfer coordinate. The excited state TDDFT potential energy profile of SA and 3ASA resulted in very flat function of the OH distance in the range ROH = 1.0-1.6 A, in contrast to the relatively deep single minimum function in the ground state. Furthermore, we obtained very shallow double minima in the excited state potential energy profile of SA and 3ASA in contrast to the single minimum observed in the previous work. The change of potential energy profile along the reaction path induced by the substitution of electron donating groups (-NH2 and -OCH3) at different sites has been investigated. Substitution at para position with respect to the phenolic OH group showed strong suppression of excited state proton dislocation compared with unsubstitued SA, while substitution at ortho position hardly affected the shape of the ESIPT curve. The TDDFT results are discussed in comparison with those of CASPT2 method.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.232-232
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• 2006

Intramolecular energy transfer in heteroleptic red phosphorescent dopant materials with mixed ligand units in one molecule was studied. 1-phenylisoquinoline(piq) and phenylpyridine(ppy) moieties were introduced as ligands for Ir based phosphorescent dopants and light emission mechanism was investigated. Intramolecular energy transfer from ppy ligand to piq ligand resulted in pure red emission without any green emission from ppy. Current efficiency of red devices was improved from 4 cd/A to 4.8 cd/A by using mixed ligand structures and deposition temperature of red dopant could be lowered by introducing ppy ligand.

• Bulletin of the Korean Chemical Society
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• v.17 no.7
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• pp.616-621
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• 1996

The transfer of excitation energy from solvent to solute in polystyrene films doped with 2-(2'-hydroxyphenyl)benzothiazole (HBT) which undergoes intramolecular proton transfer in excited electronic state has been studied by employing steady state and time-resolved fluorescence measurements. The degree of Forster overlap between donor and acceptor molecule in this system is estimated to be moderate. Energy transfer efficiency increases with solute concentration at low concentration range and levels off at high concentration. It is observed that the excimer form of polystyrene is largely involved in energy transfer process. Photostability of HBT in polystyrene to UV light is also investigated to get insight into the long wavelength absorption band of HBT which was observed upon electron radiation.

• Bulletin of the Korean Chemical Society
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• v.28 no.8
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• pp.1249-1255
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• 2007

We have investigated the photophysical properties of dansyl-N-methylaminobenzoic acid (DABAH) as a ligand and its lanthanide (Ln3+)-cored complexes (Ln3+-(DABA)3(terpy)) in order to determine the main energy transfer pathway for sensitized near infrared emission of Ln3+ ions (Ln3+ = Nd3+ and Er3+) in Ln3+- (DABA)3(terpy). The fluorescence spectrum of DABAH shows a large Stokes shift with increasing solvent polarity. This large Stokes shift might be due to the formation of a twisted intramolecular charge transfer (TICT) state, as demonstrated by the large dipole moment in the excited state. It is in good agreement with the result that the phosphorescence even in the Gd3+-cored complex based on the DABAH ligand was not observed, maybe due to the highly forbidden character of the S1 → T1 transition in the DABAH ligand. A short decay component (ca. 1 ns) was observed in Er3+-(DABA)3(terpy) whereas the fluorescence lifetimes of DABAH and its Gd3+-(DABA)3(terpy) are observed about ~10 ns. The short component could be originated from the energy transfer process between the ligand and the Ln3+ ion. Based on the fluorescence of DABAH its Ln3+- (DABA)3(terpy), the sensitization of Ln3+ luminescence in the Ln3+-(DABA)3(terpy) takes place by the energy transfer via the TICT state of DABAH in the excited singlet state rather than via the excited triplet state.

• Bulletin of the Korean Chemical Society
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• v.6 no.1
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• pp.23-29
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• 1985

The charge-transfer complexing properties of 1-methyl nicotinamide (MNA), an acceptor, and adenine, a donor, were investigated in water and SDS micellar solutions in relation to the intramolecular interaction in nicotinamide adenine dinucleotide ($NAD^+$). The spectral and thermodynamic parameters of MNA-indole and methyl viologen-adenine complex formations were determined, and the data were utilized to evaluate the charge-transfer abilities of MNA and adenine. The electron affinity of nicotinamide was estimated to be 0.28 eV from charge-transfer energy $of{\sim}300$ nm for MNA-indole. The large enhancement of MNA-indole complexation in SDS solutions by entropy effect was attributed to hydrophobic nature of indole. The complex between adenine and methyl viologen showed an absorption band peaked near 360 nm. The ionization potential of adenine was evaluated to be 8.28 eV from this. The much smaller enhancement of charge-transfer interaction involving adenine than that of indole in SDS solutions was attributed to weaker hydrophobic nature of the donor. The charge-transfer energy of 4.41 eV (280 nm) was estimated for nicotinamide-adenine complex. The spectral behaviors of $NAD^+$ were accounted to the presence of intramolecular interaction in $NAD^+$, which is only slightly enhanced in SDS solutions. The replacement of nicotinamide-adenine interaction in $NAD^+$ by intermolecular nicotinamide-indole interaction in enzyme bound $NAD^+$, and guiding role of adenine moiety in $NAD^+$ were discussed.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.495-502
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• 2006

Intramolecular energy flow and C-$H_{methyl}$ and C-$H_{ring}$ bond dissociations in vibrationally excited toluene in the collision with HF have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited toluene upon collision is not large and it increases slowly with increasing total vibrational energy content between 20,000 and 45,000 $cm ^{-1}$. Above the energy content of 45,000 $cm ^{-1}$, however, energy loss decreases. Furthermore, in the highly excited toluene, toluene gains energy from incident HF. The temperature dependence of energy loss is negligible between 200 and 400 K. Energy transfer to or from the excited methyl C-H bond occurs in strong collisions with HF transferring relatively large amount of its translational energy (>> $k_BT$) in a single step, whereas energy transfer to the ring C-H bond occurs in a series of small steps. When the total energy content $E_T$ of toluene is sufficiently high, either C-H bond can dissociate. The C-$H_{methyl}$ dissociation probability is higher than the C-$H_{ring}$ dissociation probability. The dissociation of the ring C-H bond is not the result of the intermolecular energy flow from the direct collision between the ring C-H and HF but the intramolecular flow of energy from the methyl group to the ring C-H stretch. The C-$H_{ring}$${\cdot}{\cdot}{\cdot}$HF interaction is not important in transferring energy and in turn bond dissociation.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1706-1710
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• 2005

The excited-state intramolecular proton transfer (ESIPT) fluorescence in the 2-(2'-hydroxyphenyl)benzoxazole (HBO) derivatives with different electron donor and acceptor substituents was studied by spectroscopic and theoretical methods. Changes in the electronic transition, energy levels, and orbital diagrams of HBO analogues were investigated by the semi-empirical molecular orbital calculation and were correlated with the experimental spectral position of ESIPT keto emission. It was found that the presence of substituents, regardless of their nature, resulted in the red-shifted absorption relative to HBO. However, the spectral change of the ESIPT fluorescence was differently affected by the nature of substituent: hypsochromic shift with electron donor and bathochromic shift with electron acceptor.