Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy
- NSF-PAR ID:
- 10052288
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 142
- Issue:
- 17
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 174201
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Interactions of electronic and vibrational degrees of freedom are essential for understanding excited-states relaxation pathways of molecular systems at interfaces and surfaces. Here, we present the development of interface-specific two-dimensional electronic–vibrational sum frequency generation (2D-EVSFG) spectroscopy for electronic–vibrational couplings for excited states at interfaces and surfaces. We demonstrate this 2D-EVSFG technique by investigating photoexcited interface-active ( E )-4-((4-(dihexylamino) phenyl)diazinyl)-1-methylpyridin-1- lum (AP3) molecules at the air–water interface as an example. Our 2D-EVSFG experiments show strong vibronic couplings of interfacial AP3 molecules upon photoexcitation and subsequent relaxation of a locally excited (LE) state. Time-dependent 2D-EVSFG experiments indicate that the relaxation of the LE state, S 2 , is strongly coupled with two high-frequency modes of 1,529.1 and 1,568.1 cm −1 . Quantum chemistry calculations further verify that the strong vibronic couplings of the two vibrations promote the transition from the S 2 state to the lower excited state S 1 . We believe that this development of 2D-EVSFG opens up an avenue of understanding excited-state dynamics related to interfaces and surfaces.more » « less