Volume 34 Issue 1
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Ang Xu, Yu-jie Ma, Dong Yan, Fang-fang Li, Jia-xing Liu, Feng-yan Wang. Advanced Techniques for Quantum-State Specific Reaction Dynamics of Gas Phase Metal Atoms†[J]. Chinese Journal of Chemical Physics , 2021, 34(1): 61-70. doi: 10.1063/1674-0068/cjcp2102026
Citation: Ang Xu, Yu-jie Ma, Dong Yan, Fang-fang Li, Jia-xing Liu, Feng-yan Wang. Advanced Techniques for Quantum-State Specific Reaction Dynamics of Gas Phase Metal Atoms[J]. Chinese Journal of Chemical Physics , 2021, 34(1): 61-70. doi: 10.1063/1674-0068/cjcp2102026

Advanced Techniques for Quantum-State Specific Reaction Dynamics of Gas Phase Metal Atoms

doi: 10.1063/1674-0068/cjcp2102026
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  • Corresponding author: Feng-yan Wang, E-mail: fengyanwang@fudan.edu.cn
  • Part of special topic on “the New Advanced Experimental Techniques on Chemical Physics”.
  • Received Date: 2021-02-03
  • Accepted Date: 2021-02-18
  • Publish Date: 2021-02-27
  • One of the themes of modern molecular reaction dynamics is to characterize elementary chemical reactions from "quantum state to quantum state", and the study of molecular reaction dynamics in excited states can help test the validity of modern chemical theories and provide methods to control chemical reactions. The subject of this review is to describe the recent experimental techniques used to study the reaction dynamics of metal atoms in the gas phase. Through these techniques, information such as the internal energy distribution and angular distribution of the nascent products or the three-dimensional stereodynamic reactivity can be obtained. In addition, by preparing metal atoms with specific excited electronic states or orbital arrangements, information about the reactivity of the electronic states enriches the relevant understanding of the electron transfer mechanism in metal reaction dynamics.
  • Part of special topic on “the New Advanced Experimental Techniques on Chemical Physics”.
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Advanced Techniques for Quantum-State Specific Reaction Dynamics of Gas Phase Metal Atoms

doi: 10.1063/1674-0068/cjcp2102026

Abstract: One of the themes of modern molecular reaction dynamics is to characterize elementary chemical reactions from "quantum state to quantum state", and the study of molecular reaction dynamics in excited states can help test the validity of modern chemical theories and provide methods to control chemical reactions. The subject of this review is to describe the recent experimental techniques used to study the reaction dynamics of metal atoms in the gas phase. Through these techniques, information such as the internal energy distribution and angular distribution of the nascent products or the three-dimensional stereodynamic reactivity can be obtained. In addition, by preparing metal atoms with specific excited electronic states or orbital arrangements, information about the reactivity of the electronic states enriches the relevant understanding of the electron transfer mechanism in metal reaction dynamics.

Part of special topic on “the New Advanced Experimental Techniques on Chemical Physics”.
Ang Xu, Yu-jie Ma, Dong Yan, Fang-fang Li, Jia-xing Liu, Feng-yan Wang. Advanced Techniques for Quantum-State Specific Reaction Dynamics of Gas Phase Metal Atoms†[J]. Chinese Journal of Chemical Physics , 2021, 34(1): 61-70. doi: 10.1063/1674-0068/cjcp2102026
Citation: Ang Xu, Yu-jie Ma, Dong Yan, Fang-fang Li, Jia-xing Liu, Feng-yan Wang. Advanced Techniques for Quantum-State Specific Reaction Dynamics of Gas Phase Metal Atoms[J]. Chinese Journal of Chemical Physics , 2021, 34(1): 61-70. doi: 10.1063/1674-0068/cjcp2102026
  • With the development of molecular beam and various detection techniques, especially with the emergence and development of lasers since the 1960s, the experimental studies of elementary reactions prepared in specific quantum states have provided a great deal of quantitative and qualitative information for the understanding and control of chemical reactions [1-17]. Recent studies using infrared optical parameter oscillator/amplifier system have shown that vibration excitation has a much more complex effect on reactions than just considering energy factors [5-7, 15, 16]. The effects of electronic states on chemical reactions are more complicated due to the possibility of nonadiabatic transitions between potential energy surfaces (PESs). The subject of the present review is about the techniques used in the gas-phase metal atom reactions. These reactions, such as, oxidation reactions of metal atoms, are usually fast due to the crossing between ionic and covalent potential energy surfaces, so they are called harpoon "electron" mechanism, and therefore are suitable for technique development [18, 19].

    The study on gas-phase metal reactions began in the 1930s with flame chemistry. Polanyi and coworkers studied the atomic diffusion flame of reactions between free metal atoms and halogen-containing molecules, suggesting that alkali metal atoms react quickly with many halogen species [20]. However, flame technology cannot separate the homogeneous elementary reactions from the reactions of particles formed in the gas phase, nor can it distinguish between the reactions from different electronic states. The systematic kinetic studies of gas-phase metal reactions were carried out in the fast-flowing or pseudo-static reactors. The technique used vaporization, photolysis, or discharge methods to produce gas phase metal atoms in a flow of buffer gas. The metal atomic beam enters the reaction chamber, which contains a calibrated number density of the second reactant gas of interest at low pressure. By changing the pressure, the single and double collisions can be distinguished. The energy distribution of reactants or products can be observed through chemical luminescence or laser-induced fluorescence (LIF). By comparing measurements at different temperatures or pressures, information about the reaction coefficients of metal atoms in different electronic states can be provided. However, since direct reactions and those involving long-lived intermediates also depend on temperatures and can contribute over a wide temperature range, such distinctions are not that obvious in bulk experiments. Moreover, the effect of vibration excitation on the high temperature reactions has to be considered.

    Crossed molecular beams (CMB) studies provide some of the most detailed quantitative experimental results for the single collision dynamics of elementary metal reactions with the well-controlled collision energy and precise measurement of the velocity and angular distribution of products [1, 21-23]. In 1955, Taylor and Datz used a CMB device consisting of a nickel furnace containing molten potassium, which was used as a source of potassium vapor, and of a detector using a surface ionization gauge with a tungsten and a platinum alloy filament to study the collision reaction mechanism between K and HBr [24]. In the 1960s, Herschbach led the "alkali era" by studying reaction dynamics between alkali metals and various halides through CMB experiments [25]. The reactions of alkali metal atoms with halogen species were suggested to proceed the nonadiabatic transition or crossing from covalent to ionic potential energy surfaces (harpoon "electron" mechanism), which is the main feature of distinguishing metal reactions from non-metallic reactions. Until 1969, Lee and coworkers introduced a universal CMB apparatus equipped with a skimmer between the beam source and the reaction chamber, drastically reducing the background, marking that the studies of CMB entered into the "chemical era" [26].

    The schematic diagram of the crossed beam experimental setup for metal atom reaction studies is shown in FIG. 1. The apparatus basically includes two source chambers, for producing two atomic or molecular beams, and a main chamber for reaction and detection system [27]. The technical advantages of CMB enable the reaction studies in a state-to-state manner, including the preparation of electronically excited state in the metal atom reactant, the orbital alignment experiments relative to the collision direction, and the measurement of the energy and angular distribution of their reaction products. The differential cross sections from crossed beam studies can distinguish between direct reactions and non-direct reaction with longer-lived intermediates. Using the crossed molecular beams and polarized laser excitation method, Lee and co-workers studied the reactions of the ground and electronically excited state Ba ($ ^1 $S, $ ^1 $P, $ ^3 $P, $ ^1 $D) reaction with diatomic and polyatomic molecules [28-33]. For example, Ba($ ^1 $S)+H$ _2 $O led to dominate formation of BaO+H$ _2 $, but Ba($ ^1 $D)+H$ _2 $O was primarily channeled into BaOH+H. To date, we have seen that almost all experiments with orbital-aligned atom reactions have involved alkaline earth metal atoms, mainly Ca and Ba atoms.

    Figure 1.  The schematic diagram of the crossed beam experimental setup for metal atom reaction studies. This figure is modified with permission from Ref.[27] $ © $AIP Publishing.

  • The development of metal atomic beams has been going for years accompanied with the advances in metal-containing cluster beams [34]. The gas-phase metal effusive sources are obtained by heating the desired metal above its boiling point in a high temperature oven system (temperature can be up to 2800 K) [35]. In 1981, Smalley and co-workers introduced supersonic metal cluster beams with greater intensity by using pulsed laser vaporization method [36]. In their design, a pulsed Nd: YAG laser at 532 nm was focused on the target metal rod to vaporize the metal [36, 37]. To prevent the rod from being perforated by the high-power laser, the rod was kept rotating and moving continuously through a screw drive mechanism. The short vaporization laser pulses ($ \sim $6 ns) can only vaporize a tiny amount of metal rod. This method is preferred because there is no need to heat the supersonic nozzle source and beams of even extremely refractory metals can be easily generated.

    The pulsed laser vaporization design was initially adopted by Costes et al. [38] in 1987 for the generation of supersonic metal atomic beam in crossed-beam experiments and in 1999 was modified to a "free ablation condition" without gas flow channel [39], and then followed by other groups [40, 41]. Duncan in 2012 has systemically reviewed various designs of laser vaporization [34]. As indicated in Ref.[34], a "cutaway" or "offset" source is preferred to produce more metal atoms instead of clusters. As shown FIG. 2, the "cutaway" or "offset" source without gas flow channel, proposed by Duncan [34], provides a good quality supersonic beam of single metal atoms instead of clusters. The supersonic metal atomic beam is produced by using a pulsed supersonic nozzle source for collisional cooling of hot plasma formed by laser ablation. There are many factors affecting the quality of supersonic atomic beam, including carrier gas species, backing pressure, temporal duration of the carrier gas pulse, timing between the gas pulse and vaporization laser, laser ablation wavelength, laser ablation energy, laser focus length, the distance from metal rod to the pulse valve etc. The main difference between these two designs is that the metal rod is offset out of the carrier gas line in the latter design, as shown in FIG. 2(b).

    Figure 2.  Schematic designs for a laser vaporization source (a) "cutaway" and (b) "offset". Supersonic metal atomic beam is generated by laser vaporization of metal rod and free expansion design without gas flow channel which has been employed to obtain a good quality of metal atomic beam. This figure is modified with permission from Ref.[34] $ © $AIP Publishing.

  • Earlier studies on gas-phase metal atom reactions mainly used spectroscopic detection methods, including laser-induced fluorescence (LIF) or chemiluminescence detection methods, and the consumption of transition metal atoms in the reactant can be monitored by LIF to determine the reaction rate constant [35, 38, 42-56]. Spectra, such as chemiluminescence spectroscopy, LIF spectroscopy and resonance enhanced multiphoton ionization (REMPI) spectroscopy can provide information about the energy distribution of products at high or low energy levels. However, these spectroscopic methods need to know the energy level information of the upper and lower states of molecules or atoms. Chemiluminescence or LIF methods can only be used when the detected molecules or atoms emit fluorescence.

    For example, in the laboratories of Costes or Honma, the detection technique relies or has relied on LIF to analyse the internal energy distributions of the metal atom reaction product and obtain the threshold energy through the excitation function [39, 40, 55, 57]. In the Al atom oxidation reaction Al+O$ _2 $$ \rightarrow $AlO+O at the collision energy of 12.2 kJ/mol, the internal energy state distribution of AlO is determined by the LIF spectrum of AlO product through the transition of $ B^2\Sigma^+ $-$ ^2\Sigma^+ $. The derived rotation and vibration distributions show more than that statistically expected in low vibrational and rotational levels [58].

    REMPI spectroscopy combined with mass spectrometer technique shows strong advantages in obtaining spectral information of specific species. However, REMPI is usually a multiphoton absorption process and so higher laser energy is required. For example, the (1+1) REMPI spectrum of the AlO product produced from the oxidation reaction of the Al atom at a collision energy of 12.2 kJ/mol was obtained through the $ D^2\Sigma^+ $-$ ^2\Sigma^+ $ transition, which gives the AlO rovibrational distribution similar to LIF [59].

    The use of mass spectrometers with electron impact ionizer and quadrupole mass filter to detect neutral products has facilitated the studies of a very wide range of reactions. The velocity and angular distributions of the product can be obtained by rotating the mass spectrometer detector in the beam plane, and the internal energy distribution of the product can be obtained by spectroscopy method [35, 38, 60-64]. The angular distribution in the center of mass frame can give clear information about the reaction mechanism. For example, forward scattering usually indicates a stripping reaction, backward scattering usually indicates a rebound reaction, and for long-lived collision complex formation, the forward scattering and backward scattering are symmetrically distributed. Generally, the more information provided by experimental techniques, the more we understand the dynamics and mechanisms of elementary chemical reactions.

    An important research system of metal atom reaction dynamics is to study the reaction dynamics of methane C-H activation by transition metal. In view of the importance of transition metal selective C-H activation of methane in the conversion of abundant but inert natural gas into more useful products, many related studies have been conducted [65-67]. Blomberg theoretically studied the atoms in the three transition rows and found that the rhodium atom has the lowest CH insertion reaction barrier, which was observed in the matrix separation experiment [68-72]. In the reactor at room temperature, no reaction between metal and methane was observed by kinetic techniques [48, 51, 73].

    Using rotatable source crossed molecular beams and mass spectrometer apparatus [60], Davis group studied the reaction of electronically excited Mo ($ a^5 $S$ _2 $ s$ ^1 $d$ ^5 $) with methane [74, 75]. By optically pumping the Mo atomic beam on the $ ^5 $P$ _3 $$ \leftarrow $$ ^7 $S$ _3 $ transition at 345.7 nm, the metastable Mo$ ^* $ ($ ^5 $S$ _2 $) was prepared by the transition followed by an allowed radiative decay to the desired metastable $ ^5 $S$ _2 $ state lying at 10768 cm$ ^{-1} $ (30.8 kcal/mol). In their experiment, they used the pulsed 157 nm radiation from a F$ _2 $ excimer laser in the ultrahigh vacuum region of the mass spectrometer for ionization of products MoCH$ _2 $ to improve detection sensitivity. For the ground state Mo ($ a^7 $S$ _3 $ s$ ^1 $d$ ^5 $), it has been calculated that the potential barrier for insertion into CH$ _4 $ is as high as 37.8 kcal/mol [48], and for the metastable low spin Mo$ ^* $ ($ a^5 $S$ _2 $ s$ ^1 $d$ ^5 $), the experimentally measured barrier is as small as 2.1 kcal/mol. Thus, the low spin state Mo$ ^* $ ($ a^5 $S$ _2 $ s$ ^1 $d$ ^5 $), which correlates with the ground state insertion intermediate HMoCH$ _3 $, reacts efficiently with methane. In other words, for a given total energy of electronic and translational form, it is found that electronic energy is highly effective in promoting the reaction of Mo+CH$ _4 $ whereas collisional energy is ineffective [75]. However, the chemical reaction dynamics of some transition metal ions (such as cobalt ion, nickel ion and copper ion) show that the electronic excited state is less reactive than the ground state [76]. The above results indicate that the electronic structure is correlated with the reactivity of transition metal atoms.

    Currently ion imaging technique has been used in the study of molecular reaction dynamics [77-79]. The development history of ion imaging technique began in 1987, when Chandler and Houston [80] first introduced ion imaging into the study of CH$ _3 $I photodissociation dynamics with two-dimensional position sensitive detector composed of microchannel plates and phosphor screen. In 1997, Eppink and Parker [81] improved the velocity resolution in ion imaging by removing grids in ion optics. It is called velocity map imaging (VMI), that is, ions with the same initial velocity are focused to the same point on the detector regardless of the initial position. In 2001, Kitsopoulos group [77] introduced a novel method called slicing imaging, which extended the flight time of Newton sphere to several hundreds of nanoseconds and extracted the center part for slices. The technical advantage of slice imaging is that the inverse Abel transformation is no longer required and the speed and angular distribution of products can be directly obtained from the slice image. In 2003, Liu group [78] developed a weak electronic field DC time-sliced ion velocity imaging method and applied it to crossed molecular beams research. Since 2011, Honma group and Wang group have applied time-sliced velocity map imaging technique to the studies of metal atom reactions [82-86]. Using the symmetry of the speed and angular distributions in the image, the position of the center of the Newton sphere or the origin of the center-of-mass coordinate can be easily determined, and so the velocity distribution and angular distribution in the center of mass coordinate system can be directly obtained.

    Honma et al. used velocity map imaging technique for the studies of the metal reaction systems that were studied using LIF method [59, 82, 87, 88]. The molecular beam experimental device includes a supersonic metal atomic beam, which is produced by laser vaporization of a metal rod, and the other supersonic molecular beam which crosses the metal atomic beam at the center of the ion optics. They used an OPO/OPA system for multiphoton ionization of the neutral products that are formed in the reactions. They observed the angular distributions of AlO products from the oxidation reaction of Al atoms. All angular distributions show forward and backward peaks, and the forward peak is more pronounced than the backward peak for low internal energy states. The backward peak intensity becomes comparable to the forward peak intensity for the high internal energy states. These results were compared with previous spectroscopic studies and added new insights. It is believed that the oxidation reaction of Al atoms proceeds via an intermediate and the lifetime of the intermediate is comparable to or shorter than its rotational period. Wang et al. improved the energy resolution of the experimental setup for imaging reaction dynamics of metal atoms. FIG. 3 shows the crossed beams and imaging setup with a combination of laser ablation source, which carries out a full state-to-state resolution reaction dynamics of the Al atoms by measuring the speed and angular distribution of products at different rotational quantum states. In the velocity images, the different rotational states of the AlO products and the contributions of the spin-orbit split Al ($ ^2 $P$ _{3/2, 1/2} $) reactants with an energy difference of 112 cm$ ^{-1} $ are distinguished. By accurately measuring the rotational state and velocity distribution of the AlO products, the derived impact parameter at 2.5 Å is consistent with the electron transfer distance predicted by the harpoon "electron" model $ R_C $ = $ ke^2 $/(I.E.-E.A.), where $ R_C $ is the predicted electron transfer distance, $ k $ is Coulomb constant, I.E. represents the ionization energy of metal atoms and E.A. represents the electron affinity of the oxidant molecule [41, 85].

    Figure 3.  (a) Crossed-beam and time-sliced ion velocity imaging apparatus for studying metal atomic reaction dynamics, (b) raw slice images of rotational-state selected AlO products formed from the reaction of Al+O$ _2 $$ \rightarrow $AlO+O at the collision energy of 6.07 kJ/mol, (c) corresponding speed distributions of AlO products from the raw slice images of (b). The velocity image mode is sensitive to almost zero speed near the center of the mass coordinate. This figure is based on Ref.[85] $ © $The Royal Society of Chemistry and Ref.[41] $ © $Chinese Physical Society.

    Combining crossed-beam velocity map imaging and laser state selective excitation method, Honma group studied the oxidation reactions of the gas-phase titanium atoms in electronically excited state with oxygen molecules at the collision energy of 14.3 kJ/mol [88]. Metastable excited Ti ($ a^5 $F$ _J $) was generated by an optical pumping method and the reaction products were detected by single photon-ionization followed by the time-sliced ion velocity imaging detection. The angular distributions with forward-backward peaks from the images of TiO products confirmed the mechanism proposed by the previous chemiluminescence study, and the reaction proceeds through a long-lived intermediate complex.

    We can see that the electronic excited state reactivity of metal atoms can be achieved in many technologies, such as photodissociation studies or matrix isolation infrared spectroscopy of the complex formed between the metal and the reactant [90]. Van der Waals complexes can be formed in supersonic expansion or in a matrix at low temperatures from reactants in electronically excited states. Recently, Ming-fei Zhou group [91] using matrix isolation infrared spectroscopy reported the isolation and spectroscopic characterization of eight-coordinate carbonyl complexes M(CO)$ _8 $ (where M = Ca, Sr, or Ba) in a low-temperature neon matrix (4 K). In the complexes, the alkaline earth metal atoms M (M = Ca, Sr, and Ba) are electronically excited to ($ n $-1)d states with $ n $s$ ^0 $($ n $-1)d$ ^2 $ valence electronic configuration, which allows M(d$ _\pi $)$ \rightarrow $(CO)$ _{8\pi} $ backdonation and behaves like transition metal chemistry.

  • The preparation of the quantum state involves the control of the reagent approach geometry, which is also called stereodynamic control [92]. So far, the experimental information on orientation or alignment effects mainly comes from crossed molecular beams experiments, where the steric geometry of one reactant with respect to the relative collisional direction is usually achieved by applying an external electric field, such as a strong uniform electric field or a hexapole [93-104]. Another important method is use of lasers to prepare one of the reagents whose molecular framework or electronic orbitals preferentially pointing to a certain direction in the center of mass coordinate and study the effect of that alignment or orientation on chemical reactivity. Non-spherical atomic orbitals with orbital angular momentum quantum number $ l $$ > $0 (p, d and higher l orbitals) can be controlled by absorbing linearly polarized light. The change of the polarization direction of the laser will change the direction of the rotational angular momentum vector in the upper state through the interaction with the transition dipole moments. The stereodynamic studies on metal atom reactions provide rich information on the three-dimensional geometries of reaction pathways.

    In a beam-gas scattering geometry for open-shell reagents, Rettner and Zare [105, 106] studied the reactions of electronically excited calcium atoms Ca (3s3p $ ^1 $P) with various halogen containing compounds using linearly polarized laser. The different alignments of the p orbits of the Ca atoms evolve into the ps or pp orbitals of the CaCl product, resulting in the products in two electronic states, CaCl ($ B^2\Sigma^+ $) and CaCl ($ A^2\Pi $). Ding et al. using beam-gas and chemiluminescence experiment further investigated the effect of laser-aligned Ca ($ ^1 $P) on the vibrational distributions of CaI products when colliding with CH$ _3 $I molecules [107]. The results showed that product vibrational distributions are sensitive with the reactant orbital alignment by the impact parameter.

    Lee and his colleagues [31, 33, 108, 109] comprehensively studied the different alignments of barium p orbital Ba ($ ^1 $P$ _1 $) in crossed beams experiments. As seen in FIG. 4 (a), (c) and (d), the excitation laser propagated perpendicularly to the plane of the molecular and atomic beams, allowing the p orbital to rotate in the collision plane. Alternatively, the laser propagated antiparallelly to the molecular beam, allowing the p orbital to rotate out of the collision plane. The different dependence of out-of-plane and in-plane orbital alignment observed in the reaction of Br$ _2 $ indicates that the reaction is dominated by the large impact parameter collisions. In the collisions of Ba ($ ^1 $P$ _1 $) with NO$ _2 $, for production of Ba$ ^+ $ from Ba+NO$ _2 $$ \rightarrow $Ba$ ^+ $+NO$ _2 $$ ^- $, the symmetry of the orbital does not seem to be important and the orbital is directed toward the molecule for collisions with large impact parameter. However, for the BaO$ ^+ $ from Ba+NO$ _2 $$ \rightarrow $BaO+NO channel, the alignment effects show a high sensitivity to the electron transfer or the nonadiabatic transitions between the potential energy surfaces.

    Figure 4.  Schematic views of laser aligned experiments in (a) universal crossed beams apparatus, and (b) imaging crossed beam apparatus. Illustration of alignment geometry for (c) in-plane and (d) out-of-plane rotation of the Ba ($ ^1 $P$ _1 $) orbital, (e) ($ \alpha $, $ \Phi $) geometries for the vibrationally excited C-H bond alignment of methane. In (c), the laser was aligned perpendicular to the plane of the crossed molecular and atomic beams, allowing the p orbital to rotate in the collision plane. In (d), the laser was aligned antiparallel to the molecular beam, allowing the p orbital to rotate out of the collision plane. In (e), the laser was aligned in the plane of the crossed beams and at least three independent ($ \alpha $, $ \Phi $) geometries were required for stereo control experiment: the vector $ k $ is the relative velocity of the reactants, defined as the $ z $ axis; $ k' $ is the direction of product recoil velocity, and $ \theta $ is the product scattering angle defined by $ k $ and $ k' $ in the imaging plane. The flight time axis is the $ y $ axis, which is defined by $ kxk' $. The spatial direction of the laser polarization vector $ E $ in the scattering frame is specified by the polar angle and the azimuth angle ($ \alpha $, $ \Phi $). When the $ E $ vector points to the $ x $, $ y $, or $ z $ axis, the reaction system under study can obtain three independent stereo reaction geometries. This figure is modified with permission from Ref.[33] and Ref.[110] $ © $AIP Publishing.

    Recently, a full stereo picture for the reaction of rovibrationally excited methane with chlorine atoms have been shown in detail by using time-sliced ion velocity map imaging, rotatable crossed molecular beams and linearly polarized infrared laser [7, 8, 97, 110-112]. As shown in FIG. 4 (b) and (e), by actively controlling the collisional geometry through controlling the polarization direction of the laser, the alignment-dependent slice images are obtained and the image given by different collision geometry is different. By combining the images of different collision geometry, the three-dimensional reactive structure information can be obtained. The time-sliced ion velocity imaging has shown significant technical advantage in obtaining the polarized velocity and angular distributions in polarization scattering experiments.

  • In summary, to explore the reaction mechanism of the elementary reactions, it is necessary to obtain the information of the angular distribution, velocity distribution and internal energy distribution in experiments to help theoretical calculations of the potential energy surface and reaction trajectory. The current experimental techniques for metal atom reaction studies include laser induced fluorescence, chemiluminescence, mass spectrometry, translational energy distribution and ion velocity imaging. The time-sliced ion velocity imaging technique has shown great advantages in stereo reaction studies.

    The electronic configuration of metal atoms especially transition metals is relatively complicated. However, the chemical reaction dynamics of these low-energic electronic excited states atoms is very important for understanding the activation reaction mechanism of transition metals. In the past, experimental studies on the preparation of specific electronic excited states of metal atoms and the detection of internal energy states and spatial scattering distribution of reaction products on the reactivity of bare metal atoms have provided rich information about atomic reactions, which plays an important role in the study of metal clusters and the activation of solid transition metals.

    The combination of the latest experimental methods and techniques will help us better understand the effects of electronic spin, orbital symmetry and spin-orbital coupling on the reaction dynamics, and find effective methods to control chemical reactions, and finally promote the future development of reaction dynamics research. Especially recently, with the development of laser technique and related stereodynamics methods [2-4, 7, 8, 10-15, 113], including the emergence of infrared and ultraviolet OPO/OPA sources, and the construction of high-brightness ultraviolet free electron laser light sources and infrared free electron laser sources, we have better experimental techniques and conditions in the study of excited state molecular reaction dynamics, and can provide sufficient details for state selective reaction dynamics and photochemistry to construct chemical reaction models.

  • The work was supported by the National Natural Science Foundation of China (No.21673047 and No.22073019), the Shanghai Key Laboratory Foundation of Molecular Catalysis and Innovative Materials, and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning.

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