Time-sliced Velocity Map Imaging Study on Photodissociation of Neopentyl Bromide and Tert-pentyl Bromide at 234 nm

We present a first velocity map imaging study on the 234 nm photodissociation dynamics of two carbon-chain branched alkyl bromides, neopentyl bromide （denoted as NPB） and tert- pentyl bromide （denoted as TPB）. Unlike the 234 nm photodissociation of the unbranched n-C5H11Br molecule where only a direct fission of the C-Br bond is involved, the branched NPB and TPB molecules exhibit one and two more independent dissociation pathways with much energy being decayed via an extensive excitation of the bending modes of the parent molecules prior to the C-Br bond fission. This observation strongly suggests that the dissociation coordinate for the two carbon-chain branched molecules is no longer solely ascribed to the C-Br stretching mode but rather a combination of the bending-stretching modes.

Laser Ablation Atomic Beam Apparatus with Time-Sliced Velocity Map Imaging for Studying State-to-State Metal Reaction Dynamics

We report a newly constructed laser ablation crossed molecular beam apparatus, equipped with time-sliced velocity map imaging technique, to study state-to-state metal atom reaction dynamics. Supersonic metal atomic beam is generated by laser vaporization of metal rod, and free expansion design without gas flow channel has been employed to obtain a good quality of metal atomic beam. We have chosen the crossed-beam reaction Al＋O2 to test the performance of the new apparatus. Two-rotational-states selected AIO（X^2∑＋, v=0, N and N＋I4） products can be imaged via P（N） and R（N＋14） branches of the Av=l band at the same wavelength, during （1＋1） resonance-enhanced multi-photon ionization through the AIO（D2E＋） intermediate state. In our experiment at 244.145 nm for simultaneous transitions of P（15） and R（29） branch, two rings in slice image were clearly distinguishable, corresponding to the AiO（v=0, N=IS） and AIO（v=0, N=29） states respectively. The energy difference between the two rotational levels is 403 cm^-1. The success of two states resolved in our apparatus suggests a better collisional energy resolution compared with the recent research study [J. Chem. Phys. 140, 214304 （2014）].

Photodissociation Dynamics of Dichlorodifluoromethane（CF2Cl2） around 235 nm using Time-Sliced Velocity Map Imaging Technology

Photodissociation dynamics of dichlorodifluoromethane (CF2Cl2) around 235 nm has been studied using the time-sliced velocity map imaging technology in combination with the resonance enhanced multi-photon ionization technology. By measuring the raw images of chlorine atoms which are formed via one-photon dissociation of CF2Cl2, the speed and angular distributions can be directly obtained. The speed distribution of excited-state chlorine atoms consists of high translation energy (ET) and low ET components, which are related to direct dissociation on 3Q0 state and predissociation on the ground state induced by internal conversion, respectively. The speed distribution of ground-state chlorine atoms also consists of high ET and low ET components which are related to predissociation between 3Q0 and 1Q1 states and predissociation on the ground state induced by internal conversion, respectively. Radical dissociation channel is confirmed, nevertheless, secondary dissociation and three-body dissociation channels are excluded.

Influence of the interaction volume on the kinetic energy resolution of a velocity map imaging spectrometer

We investigate the influence of the interaction volume on the energy resolution of a velocity map imaging spectrometer. The simulation results show that the axial interaction size has a significant influence on the resolution. This influence is increased for a higher kinetic energy. We further show that the radial interaction size has a minor influence on the energy resolution for the electron or ion with medium energy, but it is crucial for the resolution of the electron or ion With low kinetic energy. By tracing the flight trajectories we show how the electron or ion energy resolution is influenced by the interaction size.

Photodissociation Dynamics of Carbon Dioxide Cation via the Vibrationally Mediated A^2Hu,1/2 State： A Time-Sliced Velocity-Mapped Ion Imaging Study

We report on the photodissociation dynamics of CO2^＋ via its A2Пu,1/2 state using the scheme of [1＋1] photon excitation that is intermediated by the mode-selected A2Hu,1/2（Vl,V2,0） vibronic states. Photodissociation fragment exciation spectrum and images of photofragment CO＋ have been measured to obtain reaction dynamics parameters such as the available energy and the average translational energy. Combining with the potential energy functions of CO2^＋, the dissociation mechanism of CO2^＋ is discussed. The conformational variation of CO2^＋ from linear to bent on the photodissociation dynamics of CO2^＋ is verified.

Ion-Velocity Imaging Study of Dissociative Charge Exchange Reactions between Ar^(+)and trans-/cis-Dichloroethylene

Dissociative charge exchange re-actions between Ar^(+)ion and trans-/cis-dichloroethylene(trans-/cis-C_(2)H_(2)Cl_(2))are investi-gated with the ion-velocity imag-ing technique.The dechlorinated product C_(2)H_(2)Cl^(+)is the predomi-nant,and most of this product show the spatial distribution around the target,implying that the dissociation occurs in the large impact-parameter collision and via the energy resonant charge transfer.Meanwhile,a few C_(2)H_(2)Cl^(+)locate around the center-of-mass,which is at-tributed to the fragmentation of intimate association between C_(2)H_(2)Cl_(2)and Ar^(+)or in the small impact-parameter collision.The product C_(2)HCl_(+)exhibits the velocity distribution fea-tures similar to those of C_(2)H_(2)Cl_(+).The rarest product C_(2)HCl_(2)+shows the distributions around the molecular target,due to the quick dehydrogenation after the energy-resonant charge transfer in the large impact-parameter collision.

Imaging Isocyanic Acid Photodissociation at 193 nm:the NH(a^1△)+CO(X^1∑^+)Channel

The photodissociation dynamics of isocyanic acid （HNCO） has been studied by the time- sliced velocity map ion imaging technique at 193 nm. The NH（a1△） products were measured via （2＋1） resonance enhanced multiphoton ionization. Images have been accumulated for the NH（a1△） rotational states in the ground and vibrational excited state （v=0 and 1）. The center-of-mass translational energy distribution derived from the NH（a1△） images implies that the CO vibrational distributions are inverted for most of the measured 1NH（v｜j） internal states. The anisotropic product angular distribution observed indicates a rapid dissociation process for the N-C bond cleavage. A bimodal rotational state distribution of CO（v） has been observed, this result implies that isocyanic acid dissociates in the S1 state in two different pathways.

Imaging Reaction Dynamics of Y+SO2

The reaction dynamics of yttrium atoms with sulfur dioxide molecules at a high collision energy of 36 kcal/mol was studied using time-sliced velocity map ion imaging,crossed molecular beam and laser-ablation method.The product YO was detected via multiphoton ionization at various wavelengths in the region of 482-615 nm.The slice images of YO show a broad velocity distribution and forward-backward peaking angular distribution.The forward scattering signal is stronger than its backward distribution.This indicates that the reaction proceeds via an intermediate complex and the lifetime of the intermediate state is less than one rotational period.The formation of complex suggests that electron transfer occurs in the oxidation reaction.

Photoelectron imaging on vibrational excitation and Rydberg intermediate states in multi-photon ionization process of NH3 molecule

The ionization processes of NH3 molecule are studied by photoelectron velocity map imaging technique in a linearly polarized 400-nm femtosecond laser field. The two-dimensional photoelectron images from ammonia molecules under different laser intensities are obtained. In the slow electron region, the values of kinetic energy of photoelectrons corresponding to peaks 1, 2, 3, and 4 are 0.27, 0.86, 1.16, and 1.6 eV, respectively. With both the kinetic energy and angular distribution of photoelectrons from NH3 molecules, we can confirm that the two-photon excited intermediate Rydberg state is A^1 A2" (v2'=3) state for photoelectron peaks 2, 3, 4, and the three peaks are marked as 1223 (2 + 2), 1123 (2 + 2), and 1023 (2 + 2) multi-photon processes, respectively. Then, peak 1 is found by adding a hexapole between the source chamber and the detection chamber to realize the rotational state selection and beam focusing. Peak 1 is labeled as the 1323 (3 + 1) multi-photon process through the intermediate Rydberg state E^1A1'. The phenomena of channel switching are found in the slow electron kinetic energy distributions. Our calculations and experimental results indicate that the stretching vibrational mode of ammonia molecules varies with channels, while the umbrella vibration does not. In addition, we consider and discuss the ac-Stark effect in a strong laser field. Peaks 5 and 6 are marked as (2 + 2 + 1) and (2 + 2 + 2) above threshold ionization processes in the fast electron region.

Channel-Resolved Ultrafast Dissociation Dynamics of NO2 Molecules Studied via Femtosecond Time-Resolved Ion Imaging

The ultrafast dissociation dynamics of NO2 molecules was investigated by femtosecond laser pump-probe mass spectra and ion images.The results show that the kinetic energy release of NO+ions has two components,0.05 eV and 0.25 eV,and the possible dissociation channels have been assigned.The channel resolved transient measurement of NO^+provides a method to disentangle the contribution of ultrafast dissociation pathways,and the transient curves of NO^+ions at different kinetic energy release are fitted by a biexponential function.The fast component with a decay time of 0.25 ps is generated from the evolution of Rydberg states.The slow component is generated from two competitive channels,one of the channel is absorbing one 400nm photon to the excited state A^2B2,which has a decay time of 30.0ps,and the other slow channel is absorbing three 400nm photons to valence type Rydberg states which have a decay time less than 7.2ps.The channel and time resolved experiment present the potential of sorting out the complex ultrafast dissociation dynamics of molecules.

Ion-Neutral Photofragment Coincidence Imaging of Photodissociation Dynamics of Ionic Species

The recen tly cons true ted cryogenic cylindrical ion trap velocity map imaging spectrometer(CIT-VMI)has been upgraded for coincidence imaging of both ionic and neutral photofragments from photodissociation of ionic species.The prepared ions are cooled down in a homemade cryogenic cylindrical ion trap and then extracted for photodissociation experiments.Wi th the newly designed elec trie fields for extraction and acceleration,the ion beam can be accelerated to more than 4500 eV,which is necessary for velocity imaging of the neutral photofragments by using the position-sensitive imaging detect or.The setup has been tested by the 355 nm pho todissocia tion dynamics of the argon dimer cat ion(Ar2+).From the recorded experimen tal images of both neu tral Ar and ionic Ar+fragments,we interpret velocity resolutions of△v/vu4.6%for neutral fragments,and△v/vul.5%for ionic fragments,respectively.

Imaging HNCO Photodissociation at 201 nm:State-to-State Correlations between CO(X^1∑^+) and NH(a^1△)

The NH(a^1Δ)+CO(X^1Σ+) product channel for the photodissociation of isocyanic acid(HNCO) on the first excited singlet state S1 has been investigated by means of time-sliced ionvelocity map imaging technique at photolysis wavelengths around 201 nm. The CO productwas detected through (2+1) resonance enhanced multiphoton ionization (REMPI). Imageswere obtained for CO products formed in the ground and vibrational excited state (v=0 and v=1). The energy distributions and product angular distributions were obtained from the CO velocity imaging. The correlated NH(a^1Δ) rovibrational state distributions were determined.The vibrational branching ratio of 1NH (v=1/v=0) increases as the rotational state of CO(v=0) increases initially and decreases afterwards, which indicates a special state-tostate correlation between the 1NH and CO products. About half of the available energy was partitioned into the translational degree of freedom. The negative anisotropy parameter indicates that it is a vertical direct dissociation process.

Photodissociation Dynamics of OCS at 217 nm

The S（1D2）＋CO（X1Σ＋） product channel from photodissociation of OCS at 217 nm has been measured using the DC slice velocity map imaging （VMI） technique in combination with resonance enhanced multiphoton ionization （REMPI）. Two diflerent REMPI intermediate states （1F3 and 1P1） and several pump-probe laser polarization geometries are used to detect the angular momentum polarization of the photofragmented S（1D2）. The molecular- frame polarization parameters, as well as the laboratory-frame anisotropy parameters, for individual rotational states of co-fragment CO, are determined using two diflerent full quantum theories. The measured total kinetic energy release spectrum from photodissociation of OCS indicates two dissociation channels, corresponding to the fast and slow recoiling velocities of S（1D2）, respectively. The slow channel is concluded to originate from an initial photoexcitation to the A（1A＇） state, followed by a non-adiabatic transition to the ground state. The fast channel is found to follow a coherent excitation to A（1A＇） and B（1A＇） states, where contributions of the two states are almost equal at 217 nm. The determined alignment and anisotropy parameters further indicate that the slow channel follows an incoherent excitation, while the fast channel follows a coherent excitation to A（1A＇） and B（1A＇） states with a phase di erence of π/2.

F?(H2O)+CH3I Ligand Exchange Reaction Dynamics

Single hydration of the gas phase F^-+CH3I→CH3F reaction allows to probe solvent effects on a fundamental nucleophilic substitution reaction.At the same time,the addition of a solvent molecule opens alternative product channels.Here,we present crossed beam imaging results on the dynamics of the F^-(H2O)+CH3I→[FCH3I]^-+H2O ligand exchange pathway at collision energies between 0.3 and 2.6 eV.Product kinetic energies are constrained by the stability requirement of the weakly bound product complexes.This implies substantial internal excitation of the water molecule and disfavors effcient energy redistribution in an intermediate complex,which is reflected by the suppression of low kinetic energies as collision energy increases.At 0.3 eV,internal nucleophilic displacement is important and is discussed in light of the competing nucleophilic substitution pathways that form I^- and I^-(H2O).

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

One of the themes of modern molecular reac tion dynamics is to charac terize elementary chemical reactions from“quan tum state to quan tum stat e”,and the study of molecular reaction dynamics in excited states can help test the validi ty of modern chemical t heories and provide met hods to cont rol 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 at oms wi th specific exci ted elec tronic states or orbi tal arrangemen ts,information about the reactivity of the electronic states enriches the relevant understanding of the electron transfer mechanism in metal reaction dynamics.

Dissociative Electron Attachment to Carbon Dioxide

Our experimental progresses on the reaction dynamics of dissociative electron attachment(DEA)to carbon dioxide(CO2)are summarized in this review.First,we introduce some fundamentals about the DEA dynamics and provide an epitome about the DEAs to CO2.Second,the experimental technique developments are described,in particular,on the highresolution velocity map imaging apparatus in which we put a lot of efforts during the past two years.Third,our findings about the DEA dynamics of CO2 are surveyed and briefly compared with the others’work.At last,we give a perspective about the applications of the DEA studies and highlight the inspirations in the production of molecular oxygen on Mars and the catalytic transformations of CO2.

Photodissociation Dynamics of OCS at 207 nm:S(1D2)+CO(X^1Σ^+)Product Channel

By using the direct current slice velocity map imaging technique,the polarization experiment for S(1D2)product from the ultraviolet photodissociation of carbonyl sulfide at 207 nm was studied.The angular momentum polarization character of the photofragment S(1D2)was detected via two different resonance enhanced multiphoton ionization intermediate states,1F3 and 1P1,and four different pump-probe laser polarization geometries.The angular distribution of the corresponding CO(X^1Σ^+)coproducts was extracted and analyzed using the molecular-frame polarization and the laboratory-frame anisotropy models.The observed total kinetic energy release spectrum indicates that there are three dissociation channels,corresponding to the low,medium,and high kinetic energy.The sources of the low and medium kinetic energy channels are consistent with those of bimodal translational energy distribution at longer photolysis wavelengths.The high kinetic energy channel is a new dissociation channel arising from the direct dissociation from the single repulsive A(2^1A′)state.

Crossed Molecular Beam Study of H＋CH4 and H＋CD4 Reactions： Vibrationally Excited CH3/CD3 Product Channels

We study the H＋CH4/CD4-＋H2/HD＋CH3/CD3 reactions using the time sliced velocity map ion imaging technique. Ion images of the CH3/CD3 products were measured by the （2＋1） resonance enhanced multi-photon ionization （REMPI） detection method. Besides the CH3/CD3 products in the ground state, ion images of the vibrationally excited CH3/CD3 products were also observed at two collision energies of 0.72 and 1.06 eV. It is shown that the angular distribution of the products CH3/CD3 in vibrationally excited states gradually vary from backward scattering to sideways scattering as the collision energy increases. Compared to the CH3/CD3 products in the ground state, the CH3/CD3 products in vibrationally excited states tend to be more sideways scattered, indicating that larger impact parameters play a more important role in the vibrationally excited product channels.

High Resolution Crossed Molecular Beams Study of the H+HD→H2+D Reaction

The H+H2 reaction is the simplest chemical reaction system and has long been the prototype model in the study of reaction dynamics. Here we report a high resolution experimental investigation of the state-to-state reaction dynamics in the H+HD→H2+D reaction by using the crossed molecular beams method and velocity map ion imaging technique at the collision energy of 1.17 eV. D atom products in this reaction were probed by the near threshold 1+1'(vacuum ultraviolet+ultraviolet) laser ionization scheme. The ion image with both high angular and energy resolution were acquired. State-to-state differential cross sections was accurately derived. Fast forward scattering oscillations, relating with interference effects in the scattering process, were clearly observed for H2 products at H2(v'=0,j'=1) and H2(v'=0,j'=3) rovibrational levels. This study further demonstrates the importance of measuring high-resolution differential cross sections in the study of state-to-state reaction dynamics in the gas phase.

Vacuum Ultraviolet Photodissociation Dynamics of OCS via the F Rydberg State:theS(^(3)P_(J=2,1,0))Product Channels

Vacuum ultraviolet(VUV)photodissociation dynamics of carbonyl sulfide was investigated experimentally by using a tunable photolysis light source and the timesliced velocity map ion imaging technique.Ion images of S(^(3)P_(J=2,1,0))dissociation products were measured at five photolysis wavelengths from 133.26 nm to 139.96 nm,corresponding to the F Rydberg state of OCS.Two dissociation channels:S(^(3)P_(J))+CO(X^(1)Σ+)and S(^(3)P_(J))+CO(A^(3)Π)were observed with the former being dominant.The vibrational states of CO co-products were partially resolved in the ion images.The product total kinetic energy releases,anisotropy parameters(β),and the branching ratios of high-lying CO vibrational states were determined for the S(^(3)P_(J))+CO(X^(1)Σ^(+))channel.We found that the anisotropy parameters suddenly changed from negative to positive when OCS was excited to the higher vibrational levels of the F state.Furthermore,the anisotropy parameters for S(^(3)P_(J))products of J=2,1,0 were even different.These anomalous phenomena may result from the simultaneous existence of both parallel and perpendicular dissociation mechanisms,suggesting the involvement of other electronic states with different symmetry in the initially-excited energy region.This work provides a further understanding of the nonadiabatic couplings in the VUV photodissociation process of OCS.