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 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.

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.

Photodissociation Dynamics of CS_(2) Near 204 nm: The S(^(3)PJ)+CS(X^(1)∑^(+)) Channels

We study the phot odissociation dynamics of CS2 in the ultraviolet region using the time-sliced velocity map ion imaging technique.The S(3 Pj)+CS(X1E+)product channels were observed and identified at four wavelengths of 201.36,203.10,204.85 and 206.61 nm.In the measured images of S(3Pj=2,1,0),the vibrational states of the CS(X1E+)co-products were partially resolved and the vibrational state distributions were determined.Moreover,the product total kinetic energy releases and the anisotropic parameters were derived.The relatively small anisotropic parameter values indicate that the S(3Pj=2丄0)+CS(X1E+)channels are very likely formed via the indirect predissociation process of CS2.The study of the S(3Pj=2,1;0)+CS(X1E+)channels,which come from the spin-orbit coupling dissociation process of CS2,shows that nonadiabatic process plays a role in the ultraviolet photodissociation of CS2.

Wavelength Dependent Photodissociation of OCS via F 3^1ПRydberg State:CO(X1+)+S(1D2)Product Channel

The vacuum ultraviolet photodissociation of OCS via the F 3^1ΠRydberg states was investigated in the range of 134-140 nm by means of the time-sliced velocity map ion imaging technique.The images of S(^1D2)products from the CO(X^1Σ^+)+S(^1D2)dissociation channel were acquired at five photolysis wavelengths,corresponding to a series of symmetric stretching vibrational excitations in OCS(F 3^1Π,v1=0-4).The total translational energy distributions,vibrational populations and angular distributions of CO(X^1Σ^+,v)coproducts were derived.The analysis of experimental results suggests that the excited OCS molecules dissociate to CO(X^1Σ^+)and S(^1D2)products via non-adiabatic couplings between the upper F 3^1Πstates and the lower-lying states both in the C∞v and Cs symmetry.Furthermore,strong wavelength dependent behavior has been observed:the greatly distinct vibrational populations and angular distributions of CO(X^1Σ^+,v)products from the lower(v1=0-2)and higher(v1=3,4)vibrational states of the excited OCS(F 3^1Π,v1)demonstrate that very different mechanisms are involved in the dissociation processes.This study provides evidence for the possible contribution of vibronic coupling and the crucial role of vibronic coupling on the vacuum ultraviolet photodissociation dynamics.

Photodissociation Dynamics of OCS Near 128 nm:S(3PJ=2,1,0),S(1D2)and S(1S0)Channels

Here we report the study of the photodissociation dynamics of carbonyl sulfide in the vacuum ultraviolet region using the time-sliced velocity map ion imaging technique.Images of S(^3PJ=2,1,0),S(^1D2)and S(^1S0)products were measured at four photolysis wave-lengths of 129.32,128.14,126.99,and 126.08 nm,respectively.Four main dissociation channels:S(^3PJ=2,1,0)+CO(X^1Σ^+),S(^3PJ=2,1,0)+CO(A^3π),S(^1D2)+CO(X^1Σ^+)and S(^1S0)+CO(X^1Σ^+)channels,have been clearly observed and identified.Vibrational states of the CO co-products were partially resolved in the experimental images.From these images,the product total kinetic energy releases,the branching ratios and angular distributions of products have been derived.While the S(^3PJ=2,1,0)+CO(A^3π)product channel is formed through the adiabatic dissociation process after the excitation to the(3^1Σ^+)excited state,the results suggest that strong nonadiabatic coupling plays an important role in the formation of other three channels.

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.