New Insights into the Charge-Transfer-to-Solvent Spectrum of Aqueous Iodide: Surface versus Bulk. Bhattacharyya, D., Mizuno, H., Rizzuto, A. M., Zhang, Y., Saykally, R. J., & Bradforth, S. E. The Journal of Physical Chemistry Letters, 11(5):1656–1661, American Chemical Society (ACS), 2020. 
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Paper doi abstract bibtex Liquid phase charge-transfer-to-solvent (CTTS) transitions are important, as they serve as photochemical routes to solvated electrons. In this work, broadband deep-ultraviolet electronic sum frequency generation (DUV-ESFG) and two-photon absorption (2PA) spectroscopic techniques were used to assign and compare the nature of the aqueous iodide CTTS excitations at the air/water interface and in bulk solution. In the one-photon absorption (1PA) spectrum, excitation to the 6s Rydberg-like orbital (5p → 6s) gives rise to a pair of spin–orbit split iodine states, 2P3/2 and 2P1/2. In the 2PA spectra, the lower-energy 2P3/2 peak is absent and the observed 2PA peak, which is ∼0.14 eV blue-shifted relative to the upper 2P1/2 CTTS peak seen in 1PA, arises from 5p → 6p electronic promotion. The band observed in the ESFG spectrum is attributed to mixing of excited states involving 5p → 6p and 5p → 6s promotions caused by both vibronic coupling and the external electric field generated by asymmetric interfacial solvation.
@article{Bhattacharyya_2020,
doi = {10.1021/acs.jpclett.9b03857},
url = {https://doi.org/10.1021%2Facs.jpclett.9b03857},
year = 2020,
publisher = {American Chemical Society ({ACS})},
volume = {11},
number = {5},
pages = {1656--1661},
author = {Dhritiman Bhattacharyya and Hikaru Mizuno and Anthony M. Rizzuto and Yuyuan Zhang and Richard J. Saykally and Stephen E. Bradforth},
title = {New Insights into the Charge-Transfer-to-Solvent Spectrum of Aqueous Iodide: Surface versus Bulk},
journal = {The Journal of Physical Chemistry Letters},
abstract = {Liquid phase charge-transfer-to-solvent (CTTS) transitions are important, as they serve as photochemical routes to solvated electrons. In this work, broadband deep-ultraviolet electronic sum frequency generation (DUV-ESFG) and two-photon absorption (2PA) spectroscopic techniques were used to assign and compare the nature of the aqueous iodide CTTS excitations at the air/water interface and in bulk solution. In the one-photon absorption (1PA) spectrum, excitation to the 6s Rydberg-like orbital (5p → 6s) gives rise to a pair of spin–orbit split iodine states, 2P3/2 and 2P1/2. In the 2PA spectra, the lower-energy 2P3/2 peak is absent and the observed 2PA peak, which is ∼0.14 eV blue-shifted relative to the upper 2P1/2 CTTS peak seen in 1PA, arises from 5p → 6p electronic promotion. The band observed in the ESFG spectrum is attributed to mixing of excited states involving 5p → 6p and 5p → 6s promotions caused by both vibronic coupling and the external electric field generated by asymmetric interfacial solvation.},
bibbase_note = {<img src="https://pubs.acs.org/cms/10.1021/acs.jpclett.9b03857/asset/images/medium/jz9b03857_0003.gif">}
}
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