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1. Spatiotemporal analysis of a final-state shape resonance in interferometric photoemission from Cu(111) surfaces

   https://doi.org/10.1103/PhysRevA.100.043412  

   Ambrosio, M; Thumm, U. (October 2019, Physical review and Physical review letters index)

   Photoemission from solid targets includes the excitation and motion of electrons inside the substrate, followed by their propagation in vacuum and detection. It thus depends on the electronic band structure of the solid in the two distinct spectral domains of bound initial and continuum final states. While the imprint of the static (initial-state) valence electronic structure of solids on photoemission spectra is routinely examined in standard photoemission spectroscopy in the energy domain, state-of-the-art time-resolved photoelectron spectroscopy allows, in addition, the scrutiny of photoelectron propagation in the electronic continuum. Within a quantum-mechanical model for attosecond time-resolved interferometric photoelectron emission from solids, we calculated photoemission spectra as a function of the delay between the exciting primary attosecond pulse train and assisting infrared (IR) laser pulse. Accounting for final-state interactions of the photoelectron with the IR laser electric field and the periodic substrate, our numerical results for interferometric photoemission from the 3d-valence band of Cu(111) surfaces show a striking resonantly enhanced sideband yield at photoelectron kinetic energies near 24 eV, in conjunction with a pronounced increase of the photoelectron wave-function amplitude inside the solid on a length scale of a few nanometers. This resonant shift of final-state photoelectron-probability density towards the bulk can be interpreted as an increase in the photoelectron propagation time in the solid and is commensurate with the resonantly enhanced spectral sideband-phase shifts observed in recent two-pathway two-photon interference spectra by Kasmi et al. [Optica 4, 1492 (2017)]. 

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2. Effect of MoO ₃ buffer layer on the electronic structure of Al–BP interface

   https://doi.org/10.1088/1361-6463/ac7a70  

   Liu, Baoxing; Xie, Haipeng; Wang, Shitan; Zhao, Yuan; Liu, Yuquan; Niu, Dongmei; Gao, Yongli (June 2022, Journal of Physics D: Applied Physics)

   Abstract The interfacial modification effect of the molybdenum trioxide (MoO 3 ) buffer layer inserted between Al and black phosphorus (BP) was investigated with photoemission spectroscopy. The results show that MoO 3 buffer layer can effectively prevent the destruction of the outermost BP lattice by Al thermal deposition and change the interface electronic structure between Al and BP. At the MoO 3 /BP interface, there is an interface dipole pointing from MoO 3 to BP. During the metal deposition process, an interfacial chemical reaction between Al and MoO 3 was found. These observations would provide insight for fabricating high-performance BP-based devices. 

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3. Development of Interface-Specific Two-Dimensional Vibrational–Electronic (i2D-VE) Spectroscopy for Vibronic Couplings at Interfaces

   https://doi.org/10.3390/spectroscj3010001  

   Qian, Yuqin; Huang-Fu, Zhi-Chao; Brown, Jesse B; Rao, Yi (March 2025, Spectroscopy Journal)

   Bulk 2D electronic–vibrational (2D-EV) and 2D vibrational–electronic spectroscopies (2D-VE) were previously developed to correlate the electronic and vibrational degrees of freedom simultaneously, which allow for the study of couplings between electronic and vibrational transitions in photo-chemical systems. Such bulk-dominated methods have been used to extensively study molecular systems, providing unique information such as coherence sensitivity, molecular configurations, enhanced resolution, and correlated states and their dynamics. However, the analogy of interfacial 2D spectroscopy has fallen behind. Our recent work presented interface-specific 2D-EV spectroscopy (i2D-EV). In this work, we develop interface-specific two-dimensional vibrational–electronic spectroscopy (i2D-VE). The fourth-order spectroscopy is based on a Mach–Zehnder IR interferometer that accurately controls the time delay of an IR pump pulse pair for vibrational transitions, followed by broadband interface second-harmonic generation to probe electronic transitions. We demonstrate step-by-step how a fourth-order i2D-VE spectrum of AP3 molecules at the air/water interface was collected and analyzed. The line shape and signatures of i2D-VE peaks reveal solvent correlations and the spectral nature of vibronic couplings. Together, i2D-VE and i2D-EV spectroscopy provide coupling of different behaviors of the vibrational ground state or excited states with electronic states of molecules at interfaces and surfaces. The methodology presented here could also probe dynamic couplings of electronic and vibrational motions at interfaces and surfaces, extending the usefulness of the rich data that are obtained. 

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4. Excited-state resonance Raman spectroscopy probes the sequential two-photon excitation mechanism of a photochromic molecular switch

   https://doi.org/10.1063/5.0126974  

   Burns, Kristen H.; Quincy, Timothy J.; Elles, Christopher G. (December 2022, The Journal of Chemical Physics)

   Some diarylethene molecular switches have a low quantum yield for cycloreversion when excited by a single photon, but react more efficiently following sequential two-photon excitation. The increase in reaction efficiency depends on both the relative time delay and the wavelength of the second photon. This paper examines the wavelength-dependent mechanism for sequential excitation using excited-state resonance Raman spectroscopy to probe the ultrafast (sub-30 fs) dynamics on the upper electronic state following secondary excitation. The approach uses femtosecond stimulated Raman scattering (FSRS) to measure the time-gated, excited-state resonance Raman spectrum in resonance with two different excited-state absorption bands. The relative intensities of the Raman bands reveal the initial dynamics in the higher-lying states, Sn, by providing information on the relative gradients of the potential energy surfaces that are accessed via secondary excitation. The excited-state resonance Raman spectra reveal specific modes that become enhanced depending on the Raman excitation wavelength, 750 or 400 nm. Many of the modes that become enhanced in the 750 nm FSRS spectrum are assigned as vibrational motions localized on the central cyclohexadiene ring. Many of the modes that become enhanced in the 400 nm FSRS spectrum are assigned as motions along the conjugated backbone and peripheral phenyl rings. These observations are consistent with earlier measurements that showed higher efficiency following secondary excitation into the lower excited-state absorption band and illustrate a powerful new way to probe the ultrafast dynamics of higher-lying excited states immediately following sequential two-photon excitation. 

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5. Linear dichroism in few-photon ionization of laser-dressed helium

   https://doi.org/10.1140/epjd/s10053-021-00218-0  

   Meister, Severin; Bondy, Aaron; Schnorr, Kirsten; Augustin, Sven; Lindenblatt, Hannes; Trost, Florian; Xie, Xinhua; Braune, Markus; Manschwetus, Bastian; Schirmel, Nora; et al (July 2021, The European Physical Journal D)

   null (Ed.)

   Abstract Ionization of laser-dressed atomic helium is investigated with focus on photoelectron angular distributions stemming from two-color multi-photon excited states. The experiment combines extreme ultraviolet (XUV) with infrared (IR) radiation, while the relative polarization and the temporal delay between the pulses can be varied. By means of an XUV photon energy scan over several electronvolts, we get access to excited states in the dressed atom exhibiting various binding energies, angular momenta, and magnetic quantum numbers. Furthermore, varying the relative polarization is employed as a handle to switch on and off the population of certain states that are only accessible by two-photon excitation. In this way, photoemission can be suppressed for specific XUV photon energies. Additionally, we investigate the dependence of the photoelectron angular distributions on the IR laser intensity. At our higher IR intensities, we start leaving the simple multi-photon ionization regime. The interpretation of the experimental results is supported by numerically solving the time-dependent Schrödinger equation in a single-active-electron approximation. Graphic abstract 

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