RIKEN
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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
(END)
2020.06.24 View 14826 -
Scientists Observe the Elusive Kondo Screening Cloud
Scientists ended a 50-year quest by directly observing a quantum phenomenon
An international research group of Professor Heung-Sun Sim has ended a 50-year quest by directly observing a quantum phenomenon known as a Kondo screening cloud. This research, published in Nature on March 11, opens a novel way to engineer spin screening and entanglement. According to the research, the cloud can mediate interactions between distant spins confined in quantum dots, which is a necessary protocol for semiconductor spin-based quantum information processing. This spin-spin interaction mediated by the Kondo cloud is unique since both its strength and sign (two spins favor either parallel or anti-parallel configuration) are electrically tunable, while conventional schemes cannot reverse the sign.
This phenomenon, which is important for many physical phenomena such as dilute magnetic impurities and spin glasses, is essentially a cloud that masks magnetic impurities in a material. It was known to exist but its spatial extension had never been observed, creating controversy over whether such an extension actually existed.
Magnetism arises from a property of electrons known as spin, meaning that they have angular momentum aligned in one of either two directions, conventionally known as up and down. However, due to a phenomenon known as the Kondo effect, the spins of conduction electrons—the electrons that flow freely in a material—become entangled with a localized magnetic impurity, and effectively screen it. The strength of this spin coupling, calibrated as a temperature, is known as the Kondo temperature.
The size of the cloud is another important parameter for a material containing multiple magnetic impurities because the spins in the cloud couple with one another and mediate the coupling between magnetic impurities when the clouds overlap. This happens in various materials such as Kondo lattices, spin glasses, and high temperature superconductors.
Although the Kondo effect for a single magnetic impurity is now a text-book subject in many-body physics, detection of its key object, the Kondo cloud and its length, has remained elusive despite many attempts during the past five decades. Experiments using nuclear magnetic resonance or scanning tunneling microscopy, two common methods for understanding the structure of matter, have either shown no signature of the cloud, or demonstrated a signature only at a very short distance, less than 1 nanometer, so much shorter than the predicted cloud size, which was in the micron range.
In the present study, the authors observed a Kondo screening cloud formed by an impurity defined as a localized electron spin in a quantum dot—a type of “artificial atom”—coupled to quasi-one-dimensional conduction electrons, and then used an interferometer to measure changes in the Kondo temperature, allowing them to investigate the presence of a cloud at the interferometer end.
Essentially, they slightly perturbed the conduction electrons at a location away from the quantum dot using an electrostatic gate. The wave of conducting electrons scattered by this perturbation returned back to the quantum dot and interfered with itself. This is similar to how a wave on a water surface being scattered by a wall forms a stripe pattern. The Kondo cloud is a quantum mechanical object which acts to preserve the wave nature of electrons inside the cloud.
Even though there is no direct electrostatic influence of the perturbation on the quantum dot, this interference modifies the Kondo signature measured by electron conductance through the quantum dot if the perturbation is present inside the cloud. In the study, the researchers found that the length as well as the shape of the cloud is universally scaled by the inverse of the Kondo temperature, and that the cloud’s size and shape were in good agreement with theoretical calculations.
Professor Sim at the Department of Physics proposed the method for detecting the Kondo cloud in the co-research with the RIKEN Center for Emergent Matter Science, the City University of Hong Kong, the University of Tokyo, and Ruhr University Bochum in Germany.
Professor Sim said, “The observed spin cloud is a micrometer-size object that has quantum mechanical wave nature and entanglement. This is why the spin cloud has not been observed despite a long search. It is remarkable in a fundamental and technical point of view that such a large quantum object can now be created, controlled, and detected.
Dr. Michihisa Yamamoto of the RIKEN Center for Emergent Matter Science also said, “It is very satisfying to have been able to obtain real space image of the Kondo cloud, as it is a real breakthrough for understanding various systems containing multiple magnetic impurities. The size of the Kondo cloud in semiconductors was found to be much larger than the typical size of semiconductor devices.”
Publication:
Borzenets et al. (2020) Observation of the Kondo screening cloud. Nature, 579. pp.210-213. Available online at https://doi.org/10.1038/s41586-020-2058-6
Profile:
Heung-Sun Sim, PhD
Professor
hssim@kaist.ac.kr
https://qet.kaist.ac.kr/
Quantum Electron Correlation & Transport Theory Group (QECT Lab)
https://qc.kaist.ac.kr/index.php/group1/
Center for Quantum Coherence In COndensed Matter
Department of Physics
https://www.kaist.ac.kr
Korea Advanced Institute of Science and Technology (KAIST)
Daejeon, Republic of Korea
2020.03.13 View 13235 -
The Real Time Observation of the Birth of a Molecule
From right to left: Dr. Kyung-Hwan Kim, Professor Hyotcherl Lhee, and Jong-Gu Kim, a Ph.D. candidate
Professor Hyotcherl Lhee of the Department of Chemistry at KAIST and Japanese research teams jointly published their research results showing that they have succeeded in the direct observation of how atoms form a molecule in the online issue of Nature on February 19, 2015.
The researchers used water in which gold atoms ([Au(CN) 2- ]) are dissolved and fired X-ray pulses over the specimen in femtosecond timescales to study chemical reactions taking place among the gold atoms. They were able to examine in real time the instant process of how gold atoms bond together to become a molecule, to a trimer or tetramer state.
This direct viewing of the formation of a gold trimer complex ([Au(CN) 2- ] 3 ) will provide an opportunity to understand complex chemical and biological systems.
For details, please see the following press release that was distributed by the High Energy Accelerator Research Organization, KEK, in Japan:
Direct Observation of Bond Formations
February 18, 2015
A collaboration between researchers from KEK, the Institute for Basic Science (IBS), the Korea Advanced Institute of Science and Technology (KAIST), RIKEN, and the Japan Synchrotron Radiation Research Institute (JASRI) used the SACLA X-ray free electron laser (XFEL) facility for a real time visualization of the birth of a molecular that occurs via photoinduced formation of a chemical bonds. This achievement was published in the online version of the scientific journal “Nature” (published on 19 February 2015).
Direct “observation” of the bond making, through a chemical reaction, has been longstanding dream for chemists. However, the distance between atoms is very small, at about 100 picometer, and the bonding is completed very quickly, taking less than one picosecond (ps). Hence, previously, one could only imagine the bond formation between atoms while looking at the chemical reaction progressing in the test-tube.
In this study, the research group focused on the process of photoinduced bond formation between gold (Au) ions dissolved in water. In the ground state (S 0 state in Fig. 1) Au ions that are weakly bound to each other by an electron affinity and aligned in a bent geometry. Upon a photoexcitation, the S 0 state rapidly converts into an excited (S 1 state in Fig. 1) state where Au-Au covalent bonds are formed among Au ions aligned in a linear geometry. Subsequently, the S 1 state transforms to a triplet state (T 1 state in Fig. 1) in 1.6 ps while accompanying further contraction of Au-Au bonds by 0.1 Å. Later, the T 1 state of the trimer converts to a tetramer (tetramer state in Fig. 1) on nanosecond time scale. Finally, the Au ions returned to their original loosely interacting bent structure.
In this research, the direct observation of a very fast chemical reaction, induced by the photo-excitation, was succeeded (Fig. 2, 3). Therefore, this method is expected to be a fundamental technology for understanding the light energy conversion reaction. The research group is actively working to apply this method to the development of viable renewable energy resources, such as a photocatalysts for artificial photosynthesis using sunlight.
This research was supported by the X-ray Free Electron Laser Priority Strategy Program of the MEXT, PRESTO of the JST, and the the Innovative Areas "Artificial Photosynthesis (AnApple)" grant from the Japan Society for the Promotion of Science (JSPS).
Publication: Nature , 518 (19 February 2015)
Title: Direct observation of bond formation in solution with femtosecond X-ray scattering
Authors: K. H. Kim 1 , J. G. Kim 1 , S. Nozawa 1 , T. Sato 1 , K. Y. Oang, T. W. Kim, H. Ki, J. Jo, S. Park, C. Song, T. Sato, K. Ogawa, T. Togashi, K. Tono, M. Yabashi, T. Ishikawa, J. Kim, R. Ryoo, J. Kim, H. Ihee, S. Adachi. ※ 1: These authors contributed equally to the work.
DOI: 10.1038/nature14163
Figure 1. Structure of a gold cyano trimer complex (Au(CN) 2 - ) 3 .
Figure 2. Observed changes in the molecular structure of the gold complex
Figure 3. Schematic view of the research of photo-chemical reactions by the molecular movie
2015.02.27 View 11289