Tip-enhanced Raman spectroscopy (TERS) has experienced tremendous growth in the last 5 years. Specifically, TER imaging provided invaluable insight into spatial distribution and properties of chemical species on a surface with resolution that is otherwise unattainable by any other analytical method. Additionally, there been further development coupling ultrafast TERS hope obtaining both temporal nanometer-scale resolution. In this Perspective, we discuss several recent advances TERS,...

Tip-enhanced Raman spectroscopy (TERS) provides chemical information for adsorbates with nanoscale spatial resolution, single-molecule sensitivity, and, when combined scanning tunneling microscopy (STM), Ångstrom-scale topographic resolution. Performing TERS under ultrahigh-vacuum conditions allows pristine and atomically smooth surfaces to be maintained, while liquid He cooling minimizes surface diffusion of across the solid surface, allowing direct STM imaging. Low-temperature TER (LT-TER)...

Tip-enhanced Raman spectroscopy (TERS) combines the ability of scanning probe microscopy (SPM) to resolve atomic-scale surface features with single-molecule chemical sensitivity surface-enhanced (SERS). Here, we report additional insights into nature conformational dynamics a free-base porphyrin at room temperature adsorbed on metal surface. We have interrogated switch between two metastable surface-mediated isomers meso-tetrakis(3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP) Cu(111) At...

Nanoscale chemical imaging of a dynamic molecular phase boundary has broad implications for range problems in catalysis, surface science, and electronics. While scanning probe microscopy (SPM) is commonly used to study boundaries, its information content can be severely compromised by diffusion, irregular packing, or three-dimensional adsorbate geometry. Here, we demonstrate the simultaneous structural analysis...

Tip-enhanced Raman scattering (TERS) and optically excited tip-enhanced fluorescence (TEF) of a self-assembled porphyrin monolayer on Ag(111) are studied using an ultrahigh vacuum scanning tunneling microscope (UHV-STM). Through selectively exciting different Q-bands meso-tetrakis- (3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP), chemical information regarding vibronic states is revealed by combination theory experiment; namely, TERS time-dependent density functional (TDDFT) simulations. The...

Plasmonic near fields, wherein light is magnified and focused within nanoscale volumes, are utilized in a broad array of technologies including optoelectronics, catalysis, sensing. Within these cavities, increases temperature expected indeed have been demonstrated. Heat generation can be beneficial or detrimental for given system technique, but either case it useful to knowledge local temperatures. Surface-enhanced Raman spectroscopy (SERS), potentially down the limit single-molecule (SM)...

Tip-enhanced Raman spectroscopy (TERS) provides chemical information about adsorbates with nanoscale spatial resolution, but developments are still required in order to incorporate ultrafast temporal resolution. In this Letter, we demonstrate that a reliable TER signal of rhodamine 6G (R6G) using picosecond (ps)-pulsed excitation can be obtained ultrahigh vacuum (UHV). contrast our previous observation irreversible loss ambient TERS ( Klingsporn , J. M. ; Sonntag D. Seideman T. Van Duyne R....

Ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) combines the atomic-scale imaging capability of scanning probe microscopy with single-molecule chemical sensitivity and structural specificity surface-enhanced spectroscopy. Here, we use these techniques in combination theory to reveal insights into influence intermolecular interactions on vibrational spectra a N-N′-bis(2,6-diisopropylphenyl)-perylene-3,4:9,10-bis(dicarboximide) (PDI) self-assembled monolayer adsorbed single-crystal...

Six new uranium chalcogenides, Ba4USe6, Ba3FeUSe6, Ba3MnUSe6, Ba3MnUS6, Ba3.3Rb0.7US6, and Ba3.2K0.8US6, related to the 2H hexagonal perovskite family have been synthesized by solid-state methods at 1173 K. These isostructural compounds crystallize in K4CdCl6 structure type space group D3d6–R3̅c of trigonal system with six formula units per cell. This is remarkably flexible. The structures Ba3MnUS6 consist infinite ∞1[MUQ66–] chains (M = Fe or Mn; Q S Se) oriented along c axis that are...

We present an experimental study on the fluorescence behavior of red fluorescent proteins TagRFP-S, TagRFP-T, mCherry, mOrange2, mStrawberry, and mKO as a function pressure up to several GPa. mStrawberry show initial increase in intensity upon application above ambient conditions. At higher pressures, decreases dramatically for all under study, probably due denaturing proteins. Small blue shifts spectra with increasing were seen hinting at increased rigidity chromophore environment. In...

A series of pseudosymmetrical structures formula K10(M2OnF11-n)3X (M = V and Nb, n 2, X (F2Cl)1/3, Br, Br4/2,I4/2; M Mo, 4, Cl, Br4/2, I4/2) illustrates generation polar with the use Λ-shaped basic building units (BBUs). For a compound to belong space group, dipole moments individual species must be partially aligned. Incorporation d(0) early transition metal polyhedral BBUs into is common method create structures, owing second-order Jahn-Teller distortion these polyhedra contain. Less...

We report a systematic study performed in ultrahigh vacuum designed to identify the laser excitation regimes which plasmonically enhanced ultrashort pulses may be used nondestructively probe surface-bound molecules. A nondestructive, continuous-wave spectroscopic is monitor effects of four different femtosecond- and picosecond-pulsed beams on SER signals emanating from molecular analytes residing within fields. roles plasmonic amplification alignment with electronic transition observed...

Mn3Ta2O8, a stable targeted material with an unusual and complex cation topology in the complicated Mn–Ta–O phase space, has been grown as ≈3-cm-long single crystal via optical floating-zone technique. Single-crystal absorbance studies determine band gap 1.89 eV, which agrees value obtained from density functional theory electronic-band-structure calculations. The valence consists of hybridized Mn d–O p states, whereas bottom conduction is formed by Ta d states. Furthermore, out three...

Red plates of Cs5[U2(μ-S2)2Cl8]I were obtained in good yield from the reaction at 1173 K U, GeI2 or SnI4, and S, with CsCl flux. The compound crystallizes space group D2h25-Immm orthorhombic system Cs5[Nb2(μ-S2)2Cl8]Cl structure type. centrosymmetric [U2(μ-S2)2Cl8]4– anion has mmm symmetry two U4+ atoms separated by 3.747(1) Å. Each U atom is coordinated to four Cl S S22– groups a square-antiprismatic arrangement. polarized absorbance spectra display prominent optical anisotropy. Magnetic...

Abstract Single crystals of Cs 5 [U 2 (μ‐S ) Cl 8 ]I are obtained by solid state reaction U, GeI or SnI 4 , S, and CsCl as flux in a 1:1:3:3.5 molar ratio (C‐coated evacuated silica tubes, complex heating cooling schedule, 75 wt% yield).

Abstract Ba 4 USe 6 (I), 3 FeUSe (II), MnUSe (III), MnUS (IV), 3.3 Rb 0.7 US (V), and 3.2 K 0.8 (VI) are prepared by solid state reaction of stoichiometric amounts the elements CsCl, RbCl, KCl acting as a flux (C‐coated evacuated silica tubes, 1173 K, d; cooling to 673 at rate 2.5 K/h).

Abstract A single crystal of the title compound is prepared by optical floating‐zone technique from a feed rod obtained mixture MnO and Ta 2 O 5 in molar ratio 3:1 (1200 °C, 28 h).

Abstract Compounds (V), (VI), and (VIII) are characterized by single crystal XRD optical absorption spectroscopy.