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  • 09월 05일 17시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능
대회명 대한화학회 제120회 학술발표회 및 총회
등록일 2017년 08월 23일 10시 21분 52초
접수번호 0983
발표코드 PHYS.O-9 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간 목 10시 : 45분
발표형식 구두발표
발표분야 Physical Chemistry - Oral Presentation for Young Scholars in Physical Chemistry
저자 및 공동저자 JUNWOO KIM, Taiha Joo*
Department of Chemistry, Pohang University of Science and Technology, Korea
제목 Why is the photo-induced intersystem crossing of ruthenium(II) complex ultrafast and efficient?
내용 Highly efficient photosensitizing property of transition-metal (TM) complexes has been exploited for various applications such as photovoltaic devices and photo-catalysts. For the charge generation process to occur efficiently in such systems, electron donor must be highly populated and have longer lifetime than the charge generation time. TM complexes satisfy these conditions, as their triplet states are populated by ultrafast intersystem crossing (ISC) with extremely high quantum yield. High spin-orbit coupling (SOC) constant of TM complexes leads to the ultrafast ISC, which can be measured directly by fluorescence decay. Photophysical properties of tris(2,2’-bipyridine)ruthenium(II) (RB) have been studied extensively as a typical system of TM complexes. Although, the ultrafast ISC of Ru(II) complex has been widely studied by various spectroscopic methods, it is still unclear because of its ultrafast reaction time, which is estimated to be shorter than 50 fs. To investigate the ultrafast ISC of Ru(II) complex, we studied RB and three RB analogs by time-resolved fluorescence (TRF), transient absorption (TA), and DFT/TD-DFT calculations,. Time resolutions of TF and TA were 60 and 25 fs, respectively. We measured accurate ISC times and the photo-induced coherent nuclear wave packets of all four samples, in which the vibrational motion, symmetry, and SOC are distinct. Interestingly, the calculation and experimental results classify the four complexes into two groups. The classification into the two groups and their electronic and vibrational features reveal the correlation between the ISC and nuclear motion and the details of the ultrafast ISC mechanism.
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