Partial Photoionization Cross Sections of Chromium from the Ground and Excited States

Partial and total photoionization cross sections of iron-peak elements are important for the determination of abundances in late-type stars and nebular objects. We have investigated photoionization of neutral chromium from the ground and excited states in the low energy region from the first ionization threshold at 6.77 eV to 30 eV. Accurate descriptions of the initial bound states of Cr I and the final residual Cr II ionic states have been obtained in the multiconfiguration Hartree-Fock method together with adjustable configuration expansions and term-dependent non-orthogonal orbitals. The B-spline R-matrix method has been used for the calculation of photoionization cross sections. The 194 LS final ionic states of Cr II 3d44s, 3d34s2, 3d5, 3d44p, and 3d34s4p principal configurations have been included in the close-coupling expansion. The inclusion of all terms of these configurations has significant impact on the near-threshold resonance structures as well as on the nonresonant background cross sections. Total photoionization cross sections from the ground 3d54sa7S and excited 3d54sa5S, 3d44s2a5D, 3d54pz5P, and 3d44s4py5P states of Cr I have been compared with other available R-matrix calculation to estimate the likely uncertainties in photoionization cross sections. We analyzed the partial photoionization cross sections for leaving the residual ion in various states to identify the important scattering channels, and noted that 3d electron ionization channel becomes dominant at higher energies.

Origin of dispersive line shapes in plasmon-enhanced stimulated Raman scattering microscopy

Plasmon-enhanced stimulated Raman scattering (PESRS) microscopy has been recently developed to reach single-molecule detection limit. Unlike conventional stimulated Raman spectra, dispersive-like vibrational line shapes were observed in PESRS. Here, we propose a theoretical model together with a phasor diagram to explain the observed dispersive-like line shapes reported in our previous study. We show that the local enhanced electromagnetic field induced by the plasmonic nanostructure interferes with the molecular dipole-induced field, resulting in the dispersive profiles of PESRS. The exact shape of the profile depends on the phase difference between the plasmonic field and the molecular dipole field. We compared plasmon-enhanced stimulated Raman loss (PESRL) and plasmon-enhanced stimulated Raman gain (PESRG) signals under the same pump and Stokes laser wavelength. The PESRL and PESRG signals exhibit similar signal magnitudes, whereas their spectral line shapes show reversed dispersive profiles, which is in an excellent agreement with our theoretical prediction. Meanwhile, we verify that the nonresonant background in PESRS mainly originates from the photothermal effect. These new insights help the proper use of PESRS for nanoscale bio-imaging and ultrasensitive detection.

Surface-enhanced FAST CARS: en route to quantum nano-biophotonics

Quantum nano-biophotonics as the science of nanoscale light-matter interactions in biological systems requires developing new spectroscopic tools for addressing the challenges of detecting and disentangling weak congested optical signals. Nanoscale bio-imaging addresses the challenge of the detection of weak resonant signals from a few target biomolecules in the presence of the nonresonant background from many undesired molecules. In addition, the imaging must be performed rapidly to capture the dynamics of biological processes in living cells and tissues. Label-free non-invasive spectroscopic techniques are required to minimize the external perturbation effects on biological systems. Various approaches were developed to satisfy these requirements by increasing the selectivity and sensitivity of biomolecular detection. Coherent anti-Stokes Raman scattering (CARS) and surface-enhanced Raman scattering (SERS) spectroscopies provide many orders of magnitude enhancement of chemically specific Raman signals. Femtosecond adaptive spectroscopic techniques for CARS (FAST CARS) were developed to suppress the nonresonant background and optimize the efficiency of the coherent optical signals. This perspective focuses on the application of these techniques to nanoscale bio-imaging, discussing their advantages and limitations as well as the promising opportunities and challenges of the combined coherence and surface enhancements in surface-enhanced coherent anti-Stokes Raman scattering (SECARS) and tip-enhanced coherent anti-Stokes Raman scattering (TECARS) and the corresponding surface-enhanced FAST CARS techniques. Laser pulse shaping of near-field excitations plays an important role in achieving these goals and increasing the signal enhancement.