期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 116, 期 26, 页码 7023-7032出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp303701b
关键词
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资金
- Office of Basic Energy Sciences of the U.S. Department of Energy [DE-SC0002190]
- Camille and Henry Dreyfus New Faculty Award
- David and Lucille Packard Fellowship for Science and Engineering
Obtaining a detailed description of photochemical reactions in solution requires measuring time-evolving structural dynamics of transient chemical species on ultrafast time scales. Time-resolved vibrational spectroscopies are sensitive probes of molecular structure and dynamics in solution. In this work, we develop doubly resonant fifth-order nonlinear visible infrared spectroscopies to probe nonequilibrium vibrational dynamics among coupled high-frequency vibrations during an ultrafast charge transfer process using a heterodyne detection scheme. The method enables the simultaneous collection of third-and fifth-order signals, which respectively measure vibrational dynamics occurring on electronic ground and excited states on a femtosecond time scale. Our data collection and analysis strategy allows transient dispersed vibrational echo (t-DVE) and dispersed pump probe (t-DPP) spectra to be extracted as a function of electronic and vibrational population periods with high signal-to-noise ratio (S/N > 25). We discuss how fifth-order experiments can measure (i) time-dependent anharmonic vibrational couplings, (ii) nonequilibrium frequency frequency correlation functions, (iii) incoherent and coherent vibrational relaxation and transfer dynamics, and (iv) coherent vibrational and electronic (vibronic) coupling as a function of a photochemical reaction.
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