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Infrared & Tunneling Microscopy Capture Molecular ‘Voice’

by Sophie Lin - Technology Editor

Researchers have achieved a breakthrough in molecular observation, developing a technique to detect the unique vibrational “fingerprint” of individual molecules. This advancement, dubbed infrared-integrated STM (IRiSTM), combines infrared excitation with scanning tunneling microscopy, allowing scientists to essentially “hear” the distinct vibrational modes of a single molecule – a feat previously limited to analyzing the collective behavior of billions.

The ability to isolate and analyze the vibrations of single molecules opens up exciting possibilities in chemistry and materials science. Understanding how energy flows at the molecular level is crucial for controlling chemical reactions and designing novel materials with specific properties. This new method provides a fundamental level of insight into how vibrational energy couples to molecular motion, potentially paving the way for precise manipulation of molecular processes.

At the heart of this innovation lies the integration of two powerful techniques. Scanning tunneling microscopy (STM) is well-established for imaging surfaces at the atomic scale by measuring the quantum tunneling of electrons. Infrared spectroscopy, meanwhile, has long been used to identify molecules based on their characteristic absorption of infrared light, which excites their vibrational modes. IRiSTM cleverly combines these, using infrared light to stimulate vibrations in a molecule even as simultaneously using the STM to detect the resulting changes. This allows researchers to pinpoint the vibrational modes of a single molecule with unprecedented precision.

Shaowei Li with the infrared-integrated scanning tunneling microscopy instrument. Credit: Shaowei Li lab / UC San Diego

“Infrared spectroscopy is one of our most powerful tools, but until now it has always been an ensemble technique,” explained Shaowei Li, Assistant Professor of Chemistry at University of California San Diego, who led the research. “This gives us a way to witness, at the most fundamental level, how vibrational energy couples to molecular motion.” The findings, published in the journal Science, represent a significant step toward controlling reactions by depositing energy into a single bond and steering molecules along desired pathways.

How IRiSTM Works: A Closer Look

The process begins with directing infrared light onto a molecule adsorbed on a conductive surface. This light excites specific vibrational modes within the molecule – stretching, bending, and twisting of its chemical bonds. Simultaneously, the scanning tunneling microscope’s sharp metal tip measures changes in the electron flow between the tip and the surface. These changes are directly correlated to the vibrational motion of the molecule, providing a highly sensitive and localized measurement. The technique allows for the characterization of vibration-mediated nuclear motions of single molecules, as detailed in the Science publication.

Researchers at the University of California, San Diego have been at the forefront of developing advanced microscopy techniques. A 2023 publication in ACS Applied Optical Materials detailed function on time-resolved scanning tunneling microscopy, demonstrating the ability to observe ultrafast dynamics at the atomic scale. This builds on a foundation of expertise in manipulating and observing matter at its most fundamental level.

Implications for Future Research

The development of IRiSTM isn’t just a technical achievement; it’s a paradigm shift in how scientists approach molecular analysis. Traditional infrared spectroscopy relies on analyzing the collective vibrations of a large number of molecules, effectively averaging out the unique characteristics of each individual molecule. IRiSTM bypasses this limitation, offering a window into the behavior of single molecules in isolation. This is particularly important for studying heterogeneous systems, where molecules exist in varying environments and exhibit different behaviors.

the ability to precisely control and monitor vibrational energy at the single-molecule level has significant implications for fields like catalysis and materials design. By understanding how molecules respond to specific vibrational stimuli, researchers can potentially design catalysts that are more efficient and selective, or create materials with tailored optical and electronic properties. A related technique, described in Physical Review Letters, demonstrates infrared absorption of submonolayers of molecules on surfaces using a scanning-tunneling-microscopy-based spectroscopy technique.

Looking ahead, the researchers plan to refine the IRiSTM technique and apply it to a wider range of molecules, and materials. The ultimate goal is to develop a comprehensive understanding of how molecular vibrations govern chemical reactions and material properties, paving the way for a new era of precision control at the nanoscale.

What are your thoughts on this breakthrough? Share your comments below, and let’s discuss the potential impact of single-molecule spectroscopy.

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