Shape Effect on the Refractive Index Sensitivity at Localized Surface Plasmon Resonance Inflection Points of Single Gold Nanocubes with Vertices.

Plasmonic gold nanoparticles with sharp tips and vertices, such as gold bipyramids (AuBPs) and gold nanocubes (AuNCs), have been widely used for high-sensitivity localized surface plasmon resonance (LSPR) sensing. However, conventional LSPR sensors based on frequency shifts have a major disadvantage: the asymmetry and broadening of LSPR peaks because of instrumental, environmental, and chemical noises that limit the precise determination of shift positions. Herein, we demonstrated an alternative method to improve the efficiency of the sensors by focusing on homogeneous LSPR scattering inflection points (IFs) of single gold nanoparticles with a single resonant mode. In addition, we investigated the effect of the shape and vertices of AuNCs on the refractive index (RI) sensitivity of homogeneous LSPR IFs by comparing with gold nanospheres (AuNSs) of similar size. The results show that for both AuNCs and AuNSs, tracking homogeneous LSPR IFs allows for higher RI sensitivity than tracking the frequency shifts of the LSPR peaks. Furthermore, single AuNCs with vertices exhibited higher RI sensitivity than single AuNSs of similar size in the homogeneous LSPR IFs. Therefore, we provided a deeper insight into the RI sensitivity of homogeneous LSPR IFs of AuNCs with vertices for their use in LSPR-based biosensors.

Tuning Chemical Interface Damping: Interfacial Electronic Effects of Adsorbate Molecules and Sharp Tips of Single Gold Bipyramids.

The optimization of the localized surface plasmon resonance (LSPR)-decaying channels of hot-electrons is essential for efficient optical and photochemical processes. Understanding and having the ability to control chemical interface damping (CID) channel contributions will bring about new possibilities for tuning the efficiency of plasmonic hot-electron energy transfer in artificial devices. In this scanning electron microscopy-correlated dark-field scattering study, the CID was controlled by focusing on the electronic nature of disubstituted benzene rings acting as adsorbates, as well as the effects of sharp tips on gold bipyramids (AuBPs) with similar aspect ratios to those of gold nanorods. The results showed that the sharp tips on single AuBPs, as well as the electronic effects of the adsorbate molecules, increase the interfacial contact between the nanoparticles and adsorbate molecules. Electron withdrawing groups (EWGs) on the adsorbates induce larger homogeneous LSPR line widths compared to those of electron donating groups (EDGs). Depending on the location (ortho, meta, and para) of the EDG, the effect of benzene rings with an EDG, which was considered to be induced by sulfur atoms bound to the nanoparticle surface, is weakened by the back transfer of electrons facilitated by the difference in the availability of the electrons of the EDG. Therefore, this study reports that the CID in the LSPR total decay channels can be tuned by controlling the electron withdrawing and electron donating features of adsorbate molecules with the surface topology of metal.

α-methylation and α-fluorination electronic effects on the regioselectivity of carbonyl groups of uracil by H and triel bonds in the interaction of U, T and 5FU with HCl and TrH3 (Tr = B, Al).

Quantum chemical calculations at the ωB97XD/6-311++G(d,p) level of theory have been executed to investigate the effect of substituents via hydrogen-bonded and triel-bonded complexes between uracil (U), thymine (T) and 5-fluorouracil (5FU) with HCl for the former complexes, and with BH3 and AlH3 for the latter complexes. These calculations are supported by single-point energy calculations at MP2/6-311++G(d,p) and CCSD/6-31 + G(d,p) levels of theory, Natural Bond Orbital (NBO) and Molecular Electrostatic Potentials (MEPs) analyses, and global/local reactivity descriptors. The results reveal that triel-bonded complexes are strongly bounded than hydrogen-bonded ones, and Al-containing dimers stronger than B-containing ones. In addition, as the central triel atom grows in size, B-containing dimers (B-O triel bond) are accompanied by weak B-H⋯O unconventional H-bonds. According to local reactivity descriptors, the B-O triel bond is hard-hard interaction that indicates that the association is primarily charge controlled, while the Al-O triel bond is soft-soft interaction that is primarily orbital controlled. In both Hydrogen as well as triel-bonded complexes, the α-methylation slightly overestimates the binding strength of U, while the α-fluorination exerts the opposite role by underestimating the binding strength of U. In overall, the effect of substituents on the bond strength and thus on the regioselectivity is very small, suggesting a competition between the two carbonyl groups in terms of structures and binding energies.

Single particle study: size and chemical effects on plasmon damping at the interface between adsorbate and anisotropic gold nanorods.

Plasmon damping in gold nanorods (AuNRs) results in the broadening of the localized surface plasmon resonance (LSPR) linewidth. LSPR broadening of plasmonic nanoparticles is useful to maximize the fraction of light energy in light harvesting and energy conversion transferred to molecules attached on the surface. However, our understanding of plasmon decay channels in AuNRs is still limited, and chemical interface damping (CID) is the most poorly understood damping mechanism. Herein, to better understand plasmon damping including CID, we performed a single particle study of plasmonic anisotropic AuNRs using dark-field (DF) microscopy and spectroscopy. First, we examined the size-dependent broadening of the homogeneous LSPR linewidth of single AuNRs in water with three different aspect ratios (ARs) at a fixed diameter of 25 nm. The LSPR linewidth increased with a decrease in the AR of single AuNRs because of the reduced average distance of hot electrons to the surface. Second, we investigated the effect of refractive index variation of the surrounding medium on the LSPR linewidth in single AuNRs of three different sizes. The LSPR linewidth in single AuNRs remained almost constant regardless of their sizes while increasing the dielectric constant of the medium. Finally, we examined the effect of adsorbate thiol molecules on the homogeneous LSPR linewidth of single AuNRs in ethanol. The LSPR linewidth was broadened upon increasing the carbon chain length of 1-alkanethiol, and 4-nitrothiophenol with a strong electron withdrawing group induced a large broadening of the LSPR linewidth. Furthermore, single AuNRs with smaller ARs showed a larger broadening of the LSPR linewidth in the presence of adsorbate thiol molecules through CID. Therefore, this investigation provides a deeper insight into the size effect on plasmon damping including CID induced by the chemical interface effect in single AuNRs.

Homogeneous localized surface plasmon resonance inflection points for enhanced sensitivity and tracking plasmon damping in single gold bipyramids.

The most polarizable localized surface plasmon resonance (LSPR) longitudinal mode of anisotropic metallic nanoparticles, such as gold bipyramids (AuBPs), is of high prominence. This optical response has tremendous applications from spectroscopy to photonics and energy devices to sensing. In conventional LSPR-based sensing, broadening and asymmetry in peaks due to chemical and instrument noise hinder obtaining a precise insight on shift positions, accordingly limiting the effectiveness and impact of LSPR sensors. Further, when investigating LSPR properties, utilizing more simplistic frequency dependent dielectric-type models can aberrantly impact the reliability of fundamental properties used for designing and fabricating efficient optical devices. For instance, more approximations can effectively limit screening intra-band and inter-band (IB) electronic transition contributions and other related optical properties. With an aim to find alternative methods to further improve their efficiency, as a first report, we devoted a particular focus on LSPR scattering inflection points (IFs) of single AuBPs. The findings reveal that tracking LSPR IFs exhibit high sensitivity over their counterpart LSPR peak shift locations. In addition, we newly detected IB transition contributions near the resonance energy in the range (1.50 eV-2.00 eV) dominated by intra-band transitions. A small increase in the local RI effectively enhances the LSPR quality factor due to IB transitions. Therefore, while neglecting IB transitions in the range below 2.4 eV can work for local air refractive index (RI), in high local RI media it can be aberrantly underestimated. Demonstrated by the use of the dielectric function based on Kramers-Kronig consistent Lorentz oscillators, our findings are in good agreement with the enhancing RI sensitivity effect. The results of this investigation support the idea that tracking curvature changes of an optical signal can be effectively used for LSPR longitudinal peak RI sensing as well as damping in the local RI environment of a single AuBP.