• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.2051-2054
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• 2006

The molecular structures of the ground and lowest triplet states of 2,3-diazabicyclo[2.2.1]hept-2-ene (DBH), 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) and their fused ring derivatives are investigated with an ab initio method and the density functional theory. Unlike the singlet DBH and DBO, the azo skeletal structures of the triplet counterparts are turned out to be quite sensitive to the change of the electronic structure of the fused ring. The B3LYP C-N=N-C dihedral angles of the triplet DBH and DBO are estimated to be about 28.0 and $40.4{^{\circ}}$, respectively. The B3LYP singlet-triplet energy gaps for DBH and DBO are predicted to be 58.4 and 48.4 kcal/mol, respectively. The triplet state energy can be lowered drastically by the presence of the remote $\Pi-\Pi$ interaction as in the case of 1bb'.

• Bulletin of the Korean Chemical Society
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• v.9 no.4
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• pp.236-240
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• 1988

A thioamide, N-5-trifluoromethyl-6-methoxy-1-thionaphthoyl-N-m ethylglycine, undergoes trans${\rightleftharpoons}$cis photoisomerization around C-N bound in solution. Azulene quenching studies showed the photoisomerization to proceed via both singlet and triplet excited states.The total quantum yield of the trans${\rightarrow}$cis photoisomerization is about 0.26, 0.14 from the singlet excited state and 0.12 from the triplet excited state. Intersystem crossing and internal conversion quantum yields were calculated from sensitized photostationary state and a plausible mechanism is proposed.

• Bulletin of the Korean Chemical Society
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• v.28 no.8
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• pp.1256-1260
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• 2007

Two β-diketone derivatives bearing triphenylene (1-naphthalene-2-yl-3-triphenylen-2-yl-propane-1,3-dione (NTPD)) and naphthalene (1,3-di-naphthalene-2-yl-propane-1,3-dione (DNPD)) and their Ln(III) complexes (Ln = Er or Gd) were synthesized and their photophysical properties were investigated. The sensitized emission of Er3+ ion in Er3+-[NTPD]3(terpy) and Er3+-[DNPD]3(terpy) was observed upon excitation at absorption maximum of ligands. Their photophysical studies indicate the sensitization of Er3+ luminescence by energy transfer through the excited triplet state of β-diketone ligand. The energy transfer rate through the excited triplet state of β-diketone ligand to Er3+ ion occurs faster than that of the oxygen quenching rate.

• Journal of Photoscience
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• v.9 no.2
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• pp.70-73
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• 2002

A cyanobacteria-like organism Aaryochloris marina performs oxygenic photosynthesis with near far-red light by the use of chlorophyll d. Reaction center chlorophyll (Chl) of Photosystem (PS) II of A. marina was studied by analysis of millisecond-delayed fluorescence. Delayed fluorescence is emitted by Chi d indicating efficient energy transfer between antenna Chi d molecules and the unknown primary electron donor of PS II. P740 a reaction center Chl of PS I of A. marina is shown to give a dimer type cation, and triplet state with a D value of 245xlO$\^$-4/ cm$\^$-l/ in contrast to the 280-290 xlO$\^$-4/cm$\^$-l/ values of P700 suggesting triplet spins interacting at a 5% larger distance in P740 than in P700.

• Journal of Photoscience
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• v.2 no.2
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• pp.73-76
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• 1995

The photohydration of 1-(m-nitrophenyl)-5, 5-dimethyl-1, 3-hexadiyne (m-NDHD) affords allenyl ketone compound (1) via triplet excited state which is converted into $\beta$-dicarbonyl compound (2) through thermal hydration. The allenyl ketone is formed by the synchronous addition of water with protonation at C$_1$ indicating that m-NDHD has the reverse polarization and greater electron withdrawing effect in the triplet excited state in comparison with p-NDHD.

• Bulletin of the Korean Chemical Society
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• v.19 no.1
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• pp.93-98
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• 1998

The molecular geometries and harmonic vibrational frequencies of biphenyl in the ground and the first excited triplet states have been calculated using the Hartree-Fock and Becke-3-Lee-Yang-Parr (B3LYP) density functional methods with 6-31G* basis set. Structural change occurs from a twisted benzene-like to a planar quinone-like form upon the excitation to the first excited state. Scaled harmonic vibrational frequencies for the ground state obtained from the B3LYP calculation show good 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.1
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• pp.47-52
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• 1995

The mechanism of the photodecomposition of 2-methoxy-1,2-diphenyl diazoethane has been investigated in methanol and isoprene using time-resolved laser flash photolysis techniques. The reaction of triplet carbene which is generated from 2-methoxy-1,2-diphenyl diazoethane with methanol is believed to proceed via thermal excitation to the singlet state. The activation energy and enthalpy are consistent with a mechanism involving thermal equilibrium between the triplet and singlet state followed by the reaction of the singlet with methanol to give ether.

• Journal of Photoscience
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• v.6 no.3
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• pp.117-121
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• 1999

Photoinduced electron transfer of C60 has been studied by the laser photolysis measuring the transient absorption bands in near-IR region. The electron transfer aromatic amines via the triplet state of C60 is confirmed by the decay of the transient absorption bands of the triplet state of C60 and the rise of the anion radical of C60 and the cation radicals of amines. The rate and efficiency of electron transfer are strongly affected by the donor ability of amines and polarity of solvents. Back electron-transfer kinetics is also strongly affected by the solvent polarity.

• Journal of the Korean Chemical Society
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• v.63 no.2
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• pp.73-77
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• 2019

We compared methodologies based on the density functional theory (DFT), e.g., time-dependent DFT (TD-DFT), TD-DFT within Tamm-Dancoff approximation (TDA-DFT), and spin-unrestricted DFT (UDFT), that are usually employed to optimize the geometries of ${\pi}$-conjugated molecules in their lowest lying triplet excited ($T_1$) state. As a model system for ${\pi}$-conjugated molecules, we employed 1,2,3,4,5-pentacyano-6-phenyl-benzene. In conjunction with 6-31G(d) basis sets, we made use of gap-tuned range-separated ${\omega}B97X$ functional which is often employed recently in the calculations of molecular excited states. Near the equilibrium geometries, we found that the important difference between the geometries derived at UDFT level and those at TD-DFT or TDA-DFT methods: more stable ground-state energies but higher triplet excitation energies for UDFT derived geometries. In the studies, we discuss such differences in more detail.

• Bulletin of the Korean Chemical Society
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• v.6 no.4
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• pp.234-238
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• 1985

The photoisomerization of 5-styryl-1,3-dimethyluracil is studied with nanosecond laser flash photolysis technique at room temperature. The laser flash photolysis of E-isomer produces the transient absorption spectrum regarded as the triplet-triplet absorption, but the transient absorption of Z-isomer does not show the typical decay curve, probably due to the facile photocyclization reaction during the laser flash photolysis. Using the energy transfer method on nanosecond laser spectroscopy, the energy of the lowest triplet state for E isomer is estimated to lie between 41.8 and 47 kcal/mol. The triplet lifetime for E-isomer obtained from the decay curve of the transient absorption is ca. 93ns. The $S_1 → T_1$ intersystem crossing of E-isomer on direct excitation is relatively inefficient at room temperature supporting the singlet mechanism for direct photoisomerization.