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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Photoluminescence of Cis-Polyacetylene Semiconductor Material
Photoluminescence (PL) is one of the key experimental characterizations of optoelectronic materials, including conjugated polymers (CPs). In this study, a simplified model of an undoped cis-polyacetylene (cis-PA) oligomer was selected and used to explain the mechanism of photoluminescence (PL) of the CPs. Using a combination of the ab initio electronic structure and a time-dependent density matrix methodology, the photo-induced time-dependent excited state dynamics were computed. We explored the phonon-induced relaxation of the photoexcited state for a single oligomer of cis-PA. Here, the dissipative Redfield equation of the motion was used to compute the dissipative excited state dynamics of electronic degrees of freedom. This equation used the nonadiabatic couplings as parameters. The computed excited state dynamics showed that the relaxation rate of the electron is faster than the relaxation rate of the hole. The dissipative excited-state dynamics were combined with radiative recombination channels to predict the PL spectrum. The simulated results showed that the absorption and emission spectra both have a similar transition. The main result is that the computed PL spectrum demonstrates two mechanisms of light emission originating from (i) the inter-band transitions, corresponding to the same range of transition energies as the absorption spectrum and (ii) intra-band transitions not available in the absorption spectra. However, the dissipative Redfield equation of the motion was used to compute the electronic degrees of freedom of the nonadiabatic couplings, which helped to process the time propagation of the excited dynamic state. This excited dynamic state shows that the relaxation rate of the electron is faster than the relaxation rate of the hole, which can be used for improving organic semiconductor materials for photovoltaic and LED applications.
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- Award ID(s):
- 1944921
- NSF-PAR ID:
- 10344970
- Date Published:
- Journal Name:
- Applied Sciences
- Volume:
- 12
- Issue:
- 6
- ISSN:
- 2076-3417
- Page Range / eLocation ID:
- 2830
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/app12062830
