Probing self-associated intermolecular H-bonding using low-frequency SERS coupled with mid-IR SERS and DFT study: a case study of 2-MBA adsorbed on ZnO nanoparticles
文献信息
Om Prakash, Ranjan K. Singh
In the present study, low-frequency SERS is reported for the first time to investigate intermolecular interactions. Low-frequency SERS in the THz region (>50 cm−1) and the mid-IR region is used to probe the H-bonding interaction in 2-mercaptobenzoic acid (2-MBA) molecules adsorbed on the surface of ZnO nanoparticles. The self-association due to H-bonding leads to dimer formation of 2-MBA through carboxylic acid groups. The characteristic Raman bands of the 2-MBA dimer, H-bonded O–H stretching and out-of-plane O–H bending modes, are observed. Subsequently, this dimer formation causes the evolution of two new low-frequency modes at 90 cm−1 (shear dimer in-plane bending) and 110 cm−1 (shear dimer stretching) of intermolecular H-bonding and a blue-shift of the torsional mode of (–COOH) + (–SH). In the THz region (50–200 cm−1) the vibrational modes are blue-shifted, while in the mid-IR region the symmetric out-of-plane O–H bending is red-shifted. The present work shows that SERS can be used to study intermolecular H-bonding of molecules at very low concentrations.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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