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Surface-enhanced Raman spectroscopy (SERS), a very powerful tool for the identification of molecular species, has relied mostly on noble metal-based substrates to obtain a high enhancement factor. In this work, we demonstrate that self-driven intrinsic defects in 2D palladium di-selenide (PdSe2) dendrites grown at low temperature (280 °C) act as hotspots for high SERS enhancement. We grow 2D dendritic PdSe2 with ample intrinsic defects to exploit it for SERS application. X-ray electron spectroscopy (XPS) analysis reveals 9.3% outer layer and 4.7% interior Se vacancies. A detailed examination of atomic-scale defects revealed Se vacancy (VSe) coupled with Se–Pd–Se vacancy (VSe-Pd-Se) in monolayer PdSe2, and an array of line defects (Se vacancies) and nanopores in bilayer PdSe2 dendrites. Interestingly, our studies reveal that Se vacancy-rich PdSe2 gives rise to line defects that act like hotspots for SERS enhancement. Remarkably, the vacancy-rich dendritic PdSe2 shows a SERS enhancement factor >105 and can detect RhB at a concentration down to 10−8 M. We speculate that the topological line defects and the edge construction in PdSe2 dendrites act as metallic wire or edge, which is partly responsible for the high enhancement in the SERS signal. The high SERS sensitivity is explained on the basis of multiple charge transfer processes combined with the predicted metal-like behavior of the defected 2D PdSe2. Our conclusions are fully supported by the density functional theory calculation of the electronic density of states of the defective bilayer (2L) PdSe2, which remarkably exhibits metallic character. Being a defect-enabled SERS substrate, dendritic 2D PdSe2 fills the gap between conventional plasmonic SERS substrate and plasmon-free SERS substrate. [ABSTRACT FROM AUTHOR]

Quantum dynamical calculations are employed to study the significance of the photolysis frequency in enhancing the selectivity and yield for controlled bond breaking in HOD. The IR/UV pulse combinations are shown to provide extremely high selectivity and yield of the system.

The ultrafast high-energy nonadiabatic excited-state dynamics of the benzylidenedimethylimidazolinone chromophore dimer has been investigated using an electronic structure method coupled with on-the-fly quantitative wave function analysis to gain insight into the photophysics of hot excitons in biological systems. The dynamical simulation provides a rationalization of the behavior of the exciton in a dimer after the photoabsorption of light to higher-energy states. The results suggest that hot exciton localization within the manifold of excited states is caused by the hindrance of torsional rotation due to imidazolinone (I) or phenolate (P) bonds i.e., Φ I - or Φ P -dihedral rotation, in the monomeric units of a dimer. This hindrance arises due to weak π-π stacking interaction in the dimer, resulting in an energetically uphill excited-state barrier for Φ I - and Φ P -twisted rotation, impeding the isomerization process in the chromophore. Thus, this study highlights the potential impact of the weak π-π interaction in regulating the photodynamics of the green fluorescent protein chromophore derivatives.

Chemical substituents hold the potential to markedly influence the photochemical behavior in molecular systems and assist in gaining a comprehensive understanding of nonadiabatic phenomena. In this study, we have conducted a comparative analysis of the influence of chemical substituents on the photochemical ring-opening of 1,3-cyclohexadiene (CHD), considering four systems: CHD, 2,3-dimethylcyclohexadiene (CHD-Me2-1), 1,4-dimethylcyclohexadiene (CHD-Me2-2), and 1,2,3,4-tetramethylcyclohexadiene (CHD-Me4), using electronic structure theory calculations and nonadiabatic molecular dynamics simulations. Employing extended multistate complete active space second-order perturbation (XMS-CASPT2) theory, we optimized reactants, S 1 states, conical intersections (CI n s), and products, revealing structural and energetic variations consistent with prior research. Nonadiabatic molecular dynamics simulation was used to gain insights into photochemical dynamics at state-averaged complete active space self-consistent field (SA-CASSCF) theory. CHD-Me4 exhibited reduced carbon-carbon single bond rupture rates, responsible for ring-opening, due to substituent proximity. Further, CHD-Me2-2 and CHD-Me4 displayed prolonged excited-state relaxation times, highlighting notable substituents' impact. Analysis of kinetic energy profiles of specific carbon atoms also revealed restrained atomic displacements, particularly in CHD-Me2-2 and CHD-Me4. These findings advance our understanding of how substituents modulate photochemical reactions in cyclohexadiene derivatives, guiding new molecular design and future research.

The sensors based on graphene have shown great promise in the detection of toxic air pollutants that are detrimental to nature and create risks to human health. Many recent experimental and computational efforts have been dedicated to sensor concepts incorporating pure graphene, graphene oxide, and doped graphene. Herein, a combination of spin-polarized density functional theory (DFT) with van der Waals correction and ab initio molecular dynamics (AIMD) approaches are utilized to assess the gas sensing potential of pyridinic dominance N-doped graphene (PNG) toward SO 2 detection. The potential of PNG systems as SO 2 sensing can be explored through an in-depth analysis of adsorption energies, electronic parameters, charge transfer, selectivity, and thermal stability. It is further demonstrated that external strains and the modulation of external electric fields are two effective ways to modify the adsorption strength. In light of these findings, our studies suggest that PNG monolayers have the potential to be an essential substrate for the detection of SO 2 .