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Title: Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy
NSF-PAR ID:
10052288
Author(s) / Creator(s):
 ;  ;  ;  
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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  1. 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. 
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