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Every Moment of Ultrafast Chemical Bonding Now Captured on Film
- The emerging moment of bond formation, two separate bonding steps, and subsequent vibrational motions were visualized. -
< Emergence of molecular vibrations and the evolution to covalent bonds observed in the research. Video Credit: KEK IMSS >
A team of South Korean researchers led by Professor Hyotcherl Ihee from the Department of Chemistry at KAIST reported the direct observation of the birthing moment of chemical bonds by tracking real-time atomic positions in the molecule. Professor Ihee, who also serves as Associate Director of the Center for Nanomaterials and Chemical Reactions at the Institute for Basic Science (IBS), conducted this study in collaboration with scientists at the Institute of Materials Structure Science of High Energy Accelerator Research Organization (KEK IMSS, Japan), RIKEN (Japan), and Pohang Accelerator Laboratory (PAL, South Korea). This work was published in Nature on June 24.
Targeted cancer drugs work by striking a tight bond between cancer cell and specific molecular targets that are involved in the growth and spread of cancer. Detailed images of such chemical bonding sites or pathways can provide key information necessary for maximizing the efficacy of oncogene treatments. However, atomic movements in a molecule have never been captured in the middle of the action, not even for an extremely simple molecule such as a triatomic molecule, made of only three atoms.
Professor Ihee's group and their international collaborators finally succeeded in capturing the ongoing reaction process of the chemical bond formation in the gold trimer. "The femtosecond-resolution images revealed that such molecular events took place in two separate stages, not simultaneously as previously assumed," says Professor Ihee, the corresponding author of the study. "The atoms in the gold trimer complex atoms remain in motion even after the chemical bonding is complete. The distance between the atoms increased and decreased periodically, exhibiting the molecular vibration. These visualized molecular vibrations allowed us to name the characteristic motion of each observed vibrational mode." adds Professor Ihee.
Atoms move extremely fast at a scale of femtosecond (fs) ― quadrillionths (or millionths of a billionth) of a second. Its movement is minute in the level of angstrom equal to one ten-billionth of a meter. They are especially elusive during the transition state where reaction intermediates are transitioning from reactants to products in a flash. The KAIST-IBS research team made this experimentally challenging task possible by using femtosecond x-ray liquidography (solution scattering). This experimental technique combines laser photolysis and x-ray scattering techniques. When a laser pulse strikes the sample, X-rays scatter and initiate the chemical bond formation reaction in the gold trimer complex. Femtosecond x-ray pulses obtained from a special light source called an x-ray free-electron laser (XFEL) were used to interrogate the bond-forming process. The experiments were performed at two XFEL facilities (4th generation linear accelerator) that are PAL-XFEL in South Korea and SACLA in Japan, and this study was conducted in collaboration with researchers from KEK IMSS, PAL, RIKEN, and the Japan Synchrotron Radiation Research Institute (JASRI).
Scattered waves from each atom interfere with each other and thus their x-ray scattering images are characterized by specific travel directions. The KAIST-IBS research team traced real-time positions of the three gold atoms over time by analyzing x-ray scattering images, which are determined by a three-dimensional structure of a molecule. Structural changes in the molecule complex resulted in multiple characteristic scattering images over time. When a molecule is excited by a laser pulse, multiple vibrational quantum states are simultaneously excited. The superposition of several excited vibrational quantum states is called a wave packet. The researchers tracked the wave packet in three-dimensional nuclear coordinates and found that the first half round of chemical bonding was formed within 35 fs after photoexcitation. The second half of the reaction followed within 360 fs to complete the entire reaction dynamics.
They also accurately illustrated molecular vibration motions in both temporal- and spatial-wise. This is quite a remarkable feat considering that such an ultrafast speed and a minute length of motion are quite challenging conditions for acquiring precise experimental data.
In this study, the KAIST-IBS research team improved upon their 2015 study published by Nature. In the previous study in 2015, the speed of the x-ray camera (time resolution) was limited to 500 fs, and the molecular structure had already changed to be linear with two chemical bonds within 500 fs. In this study, the progress of the bond formation and bent-to-linear structural transformation could be observed in real time, thanks to the improvement time resolution down to 100 fs. Thereby, the asynchronous bond formation mechanism in which two chemical bonds are formed in 35 fs and 360 fs, respectively, and the bent-to-linear transformation completed in 335 fs were visualized. In short, in addition to observing the beginning and end of chemical reactions, they reported every moment of the intermediate, ongoing rearrangement of nuclear configurations with dramatically improved experimental and analytical methods.
They will push this method of 'real-time tracking of atomic positions in a molecule and molecular vibration using femtosecond x-ray scattering' to reveal the mechanisms of organic and inorganic catalytic reactions and reactions involving proteins in the human body. "By directly tracking the molecular vibrations and real-time positions of all atoms in a molecule in the middle of reaction, we will be able to uncover mechanisms of various unknown organic and inorganic catalytic reactions and biochemical reactions," notes Dr. Jong Goo Kim, the lead author of the study.
Publications:
Kim, J. G., et al. (2020) ‘Mapping the emergence of molecular vibrations mediating bond formation’. Nature. Volume 582. Page 520-524. Available online at https://doi.org/10.1038/s41586-020-2417-3
Profile: Hyotcherl Ihee, Ph.D.
Professor
hyotcherl.ihee@kaist.ac.kr
http://time.kaist.ac.kr/
Ihee Laboratory
Department of Chemistry
KAIST
https://www.kaist.ac.kr
Daejeon 34141, Korea
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2020.06.24 View 24558 -
Nature Photonics, a peer-reviewed scientific journal, released a paper written by a KAIST research team on the time-of-flight measurement.
Professor Seung-Woo Kim of the Mechanical Engineering Department, KAIST, and his research team published the result of their study on the measurement of 1 nanometer (nm) precision.
“The time-of-flight of light pulses has long been used as a direct measure of distance, but state-of-the-art measurement precision using conventional light pulses or microwaves peaks at only several hundreds of micrometers. Here, we improve the time-of-flight precision to the nanometer regime by timing femtosecond pulses through phase-locking control of the pulse repetition rate using the optical cross-correlation technique,” Professor Kim said.
According to the experiment conducted by the research team, “An Allan deviation of 117 nm in measuring a 700m distance in air at a sampling rate of 5 millisecond (ms) once the pulse repetition is phased-locked, which reduces to 7 nm as the averaging time increases to 1 second (s).”
When measuring an object located in a far distance, a laser beam is projected to the object, and the reflected light is analyzed; the light is then converted into an electric signal to calculate the distance. In so doing, Professor Kim said, the conventional method of measurement creates at least 1 mm of deviation.
He argues, “This enhanced capability is maintained at long range without periodic ambiguity, and is well suited to lidar applications. This method could also be applied to future space missions involving formation-flying satellites for synthetic aperture imaging and remote experiments related to general relativity theory."
Nature Photonics published the article online on August 8, 2010.
2010.08.18 View 17852 -
Two KAIST Professors Elected Fellows of APS
Profs. Sung-Chul Shin and Chang-Hee Nam of the Department of Physics, KAIST, have recently been elected the 2009 fellows of the American Physical Society (APS), university officials said on Tuesday (Dec. 2).
The APS fellowship is a prestigious recognition of the two professors" outstanding academic achievements in the field of physics, the officials said. The selection criteria are known to be extremely stringent and only a small fraction of APS members become fellows.
Prof. Shin was cited for his pioneering contributions to the understanding of magnetization reversal dynamics, in particular critical scaling behavior of Barkhausen avalanches of 2D ferromagnets, and discovery of novel magnetic thin films and multilayers for high-density data storage.
Prof. Nam was recognized for his contributions to the theory and experiments of physical processes of high harmonic generation for the development of attosecond coherent x-ray sources and related femtosecond laser technology.
The American Physical Society, founded in 1899, is the world"s second largest organization of physicists, behind the Deutsche Physikalische Gesellschaft. It has 46,000 members across the world.
2008.12.04 View 20239 -
New System to Generate Extreme-Ultraviolet Light Developed
A KAIST research team led by Prof. Seung-Woo Kim of the Mechanical Engineering Department developed a new system for generating coherent extreme-ultraviolet (EUV) light, school authorities announced on June 5.
The new system comes in a metallic nano-structure consisting of a two-dimensional array of gold "bow tie" elements on a sapphire plate. The new process was featured in the British journal Nature on June 5.
The properties of coherent EUV light make it a prime candidate for exciting technological applications. But, at present, the equipment needed to generate the short-wavelength light is costly and bulky. The system developed by Prof. Kim"s research team is expected to reduce both cost and bulk.
The new system uses the conventional principle of high-harmonic generation via the interaction of a femtosecond laser pulse with a gas, but adopts the novel concept of amplifying light by way of local plasmon field enhancement, according to the research team.
2008.06.10 View 18557