• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.1931-1932
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• 2005

• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.298-302
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• 1989

The strengths of two-photon transitions from the ground state to excited vibronic states in benzene are calculated by using the CNDO/2-U wave functions. The role of vibronic coupling in two-photon absorption process is discussed. The $A_{1{\bar{g}}}-A_{2g}^+$ two-photon transitions, which are forbidden by the identity-forbidden selection rule in single frequency two-photon absorption, are too weak to be experimentally observed even when two photons of different energies are used. It is because the transitions are forbidden also by the pseudo-parity selection rule which are applicable for alternant hydrocarbons such as benzene. It is also shown that the vibronic coupling is not very effective in altering the pseudo-parity property of the electronic state. The strength of the vibronically induced two-photon absorption is strongly affected by the presence of an electronic state from which two-photon absorption can borrow the intensity. It is pointed out that the pseudo-parity selection rule may be violated in such cases.

• Macromolecular Research
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• v.9 no.2
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• pp.116-121
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• 2001

A series of poly(1,4-phenylenevinylene-alt-3-alkyl-2,5-thienylenevinylene)s (alkyl = hexyl [PPV-alt-6-TV] and octyl (PPV-alt-8-TV] group) have been synthesized by the Heck coupling reaction. These polymers were characterized using $^1$H-NMR, FT-IR spectroscopy, and thermogravimetric analysis (TCA). They are solvent processible and have obviously copolymeric structure. The photophysical properties of the polymers were investigated using UV-visible and steady-state photoluminescence(PL) spectroscopy. We studied the change of light-emitting properties by incorporating the thiophene group into the PPV polymer backbone using alternating copolymer system. The properties of two synthesized polymers are very similar, but they exhibited apparent changes of light-emitting properties compared with other PPV backbone based polymers. The broad absorption bands from 350 to 570 nm are due to $\pi$-$\pi$* transitions of the polyconjugated systems. The absorption maxima of the two polymers were found at about 452 and 448 nm for PPV-alt-6-TV and PPV-alt-8-TV, respectively. The copolymers showed broad PL spectra between 550 and 700 nm without vibronic bands and PL emission maxima of PPV-alt-6-TV and PPV-alt-8-TV are about 620 and 605 nm, respectively. The copolymers exhibited the red emission (PPValt-6-TV), but more red shifted emissions are needed to obtain real red color.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.257-258
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• 2012

The SERS spectra of 4-aminobenzenethiol (ABT) have served as the "probe" molecule, which have helped spectroscopists to build up the electromagnetic (EM) and chemical (CHEM) enhancement mechanisms. In particular, the b2-peaks (9b, 3, and 19b) of the SERS spectra of ABT have been attributed to arise from the vibronic charge-transfer (CT) between Au or Ag surface and the ABT. Quite recently, however, Tian and co-workers [1] claimed that the b2-peaks are not the CT-enhanced spectra of ABT. Instead, these peaks arise from the 4,4'-dimercaptoazobenzenes (DMABs) that are produced by the oxidative coupling of two ABTs. Their claim is under intense debate currently. Herein, we studied spatially and temporally resolved SERS spectra of ABTs on Ag thin film (thickness of 10 nm), to investigate such claim. Herein, we present a series of additional evidences that strongly support that the b2 intensities of ABTs do not arise from the CT-enhancement: (1) the b2-peaks can be locally "activated" (i. e. turned on) irreversibly with focused laser radiation; (2) the TOF-SIM spectrometry on the activated region show depletion of ABT-Ag+ ions; and finally (3) the spatially resolved FT-IR spectra of the activated region show two pronounced peaks at 1377 cm-1 and 1460 cm-1, both of which can be assigned to the stretching mode of N=N bond. While the result does not disprove the existence of CT or CHEM enhancement in general, the results do show that previous interpretations of the spectra of ABTs should be re-interpreted.