Showing papers by "Richard J. Saykally published in 2020"
TL;DR: 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.
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.
14 citations
TL;DR: In this article, the authors describe recent technological advances which have enabled new experiments on liquid carbon samples, prepared with laser melting and shock compression techniques, and describe their properties and properties.
11 citations
TL;DR: In this paper, a reexamination of the π→π* transition of nitrite at the air/water interface reveals that the interfacial |χ(2)|2-spectrum is strikingly similar to the bulk absorption spectrum.
2 citations
TL;DR: In this article, the authors used the FERMI free electron laser (FEL) to measure the reflectivity of amorphous carbon (a-C) in the ultrafast time-resolved extreme ultraviolet (EUV) reflectivity measurements of a-C. The results showed that a significant increase in the characteristic time was observed upon increasing the probing depth due to hydrodynamic expansion and consequent destruction of the excited region.
Abstract: Ultrafast time-resolved extreme ultraviolet (EUV) reflectivity measurements of optically pumped amorphous carbon (a-C) have been performed with the FERMI free electron laser (FEL). This work extends the energy range used in previous reflectivity studies and adds polarization dependence. The EUV probe is known to be sensitive to lattice dynamics, since in this range the reflectivity is essentially unaffected by the photo-excited surface plasma. The exploitation of both s- and p-polarized EUV radiation permits variation of the penetration depth of the probe; a significant increase in the characteristic time is observed upon increasing the probing depth (1 vs. 5 ps) due to hydrodynamic expansion and consequent destruction of the excited region, implying that there is only a short window during which the probed region is in the isochoric regime. A weak wavelength dependence of the reflectivity is found, consistent with previous measurements and implying a maximum electronic temperature of 0.8 eV ± 0.4.