Real-Time Probing of Ion Pairing Dynamics with 2DIR Spectroscopy

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초록

Chemical exchange two-dimensional infrared (2DIR) spectroscopy is applied to investigate ion pairing dynamics occurring on picosecond timescales. SeCN- ion is used as a vibrational probe. The SeCN- ion dissolved in N,N-dimethyl formamide (DMF) has a sufficiently long vibrational lifetime and can form a contact ion pair with Li+ ion in DMF. The CN stretch frequency of the contact ion pair is significantly blue-shifted from that of free SeCN- so the free SeCN- ion can be spectrally distinct from the contact ion pair in DMF. Therefore, we were able to directly monitor the ion pairing dynamics of Li+ and SeCN- in real time by using ultrafast 2DIR spectroscopy. As a result, we have determined the dissociation time constant of the LiSeCN contact ion pair to be 420 +/- 40 ps.

키워드

chemical exchange; ion pairing dynamics; ion pairs; ir spectroscopy; vibrational probe; HYDROGEN-BOND DYNAMICS; INFRARED-SPECTROSCOPY; ULTRAFAST DYNAMICS; 2D-IR SPECTROSCOPY; N-METHYLACETAMIDE; AQUEOUS-SOLUTIONS; IR SPECTROSCOPY; WATER; PROTEINS; EXCHANGE
제목
Real-Time Probing of Ion Pairing Dynamics with 2DIR Spectroscopy
저자
Park, Kwang-Hee; Choi, Seung Ryul; Choi, Jun-Ho; Park, Sungnam; Cho, Minhaeng
DOI
10.1002/cphc.201000595
발행일
2010-12-03
유형
Article
저널명
ChemPhysChem
권
11
호
17
페이지
3632 ~ 3637