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.

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.

A Quantum Wavepacket Study of State-to-State Photodissociation Dynamics of HOBr/DOBr

Photodissociation of HOBr is an important step in the reaction network of the depletion of ozone in stratosphere.Here,we report the first three-dimensional potential energy surfaces for the lowest three singlet states for HOBr,based on high level multi reference configuration interaction calculations.Quantum dynamics calculations are performed with a real wavepacket method,yielding not only absorption spectra but also internal state and angular distributions of the photodissociation fragments.Our results agree quantitatively with the measured total absorption cross sections of HOBr in the ultraviolet region and reproduce well the observed vibrationally cold and rotationally hot OH/OD fragments via photodissociation of HOBr/DOBr at 266 nm.In addition,we predict that the recoil anisotropy parameters for OH/OD are close to the limiting value of a parallel transition,suggesting a rapid dissociation process at 266 nm following an in-plane transition from the ground state(1^1A')to the 21A'state.This is consistent with the experimental conclusion derived from the measured rotational alignment.However,spin and electronic angular momenta need to be taken into account in the future to achieve a more quantitative agreement with experiment.Our work is expected to motivate further experimental investigations for this benchmark system.

Systematical Study on Photodissociation Dynamics of BrCN from 225 nm to 260 nm

The photodissociation dynamics of Br-C bond cleavage for BrCN in the wavelength region from 225 nm to 260 nm has been studied by our homebuilt time-slice velocity-map imaging setup.The images for both of the ground state Br(^(2)P_(3/2))and spin-orbit excited Br^(*)(^(2)P_(1/2))channels are obtained at several photodissociation wavelengths.From the analysis of the translational energy release spectra,the detailed vibrational and rotational distributions of CN products have been measured for both of the Br and Br^(*) channels.It is found that the internal excitation of the CN products for the Br^(*) channel is colder than that for the Br channel.The most populated vibrational levels of the CN products are v=0 and 1 for the Br and Br^(*) channels,respectively.For the Br channel,the photodissociation dynamics at longer wavelengths are found to be different from those at shorter wavelengths,as revealed by their dramatically different vibrational and rotational excitations of the CN products.

UV Photodissociation Dynamics of Nitric Acid： The Hydroxyl Elimination Channel

Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected by （2＋1） resonance enhanced multiphoton ionization via the D^2∑^- electronic state. The total kinetic energy spectra of the OH＋NO2 channel from the photolysis of HONO2 show that both ：NO2（X2A1） and NO2（A2B2） channels are present, suggesting that both 1^1A″ and 2^1A″ excited electronic states of HONO2 are involved in the excitation. The parallel angular distributions suggest that the dissociation of the nitric acid is a fast process in comparison with the rotational period of the HNO3 molecule. The anisotropy parameter β for the hydroxyl elimination channel is found to be dependent on the OH product rotational state as well as the photolysis energy.

Theoretical Investigations on Photodissociation Dynamics of Deuterated Alkyl Halides CD_(3)CH_(2)F

The product branching ratio between different products in multichannel reactions is as important as the overall rate of reaction,both in terms of practical applications(e.g.models of combustion or atmosphere chemistry)in understanding the fundamental mechanisms of such chemical reactions.A global ground state potential energy surface for the dissociation reaction of deuterated alkyl halide CD_(3)CH_(2)F was computed at the CCSD(T)/CBS//B3 LYP/aug-cc-p VDZ level of theory for all species.The decomposition of CD_(3)CH_(2)F is controversial concerning C-F bond dissociation reaction and molecular(HF,DF,H_(2),D_(2),HD)elimination reaction.RiceRamsperger-Kassel-Marcus(RRKM)calculations were applied to compute the rate constants for individual reaction steps and the relative product branching ratios for the dissociation products were calculated using the steady-state approach.At the different energies studied,the RRKM method predicts that the main channel for DF or HF elimination from1,2-elimination of CD_(3)CH_(2)F is through a four-center transition state,whereas D_(2) or H_(2) elimination from 1,1-elimination of CD_(3)CH_(2)F occurs through a direct three-center elimination.At 266,248,and 193 nm photodissociation,the main product CD_(2)CH_(2)+DF branching ratios are computed to be 96.57%,91.47%,and 48.52%,respectively;however,at 157 nm photodissociation,the product branching ratio is computed to be 16.11%.Based on these transition state structures and energies,the following photodissociation mechanisms are suggested:at 266,248,193 nm,CD_(3)CH_(2)F→absorption of a photon→TS5→the formation of the major product CD_(2)CH_(2)+DF;at 157 nm,CD_(3)CH_(2)F→absorption of a photon→D/F interchange of TS1→CDH_(2)CDF→H/F interchange of TS2→CHD_(2)CHDF→the formation of the major product CHD_(2)+CHDF.

Photodissociation Dynamics of Methanol and Ethanol at 157 nm

157 nm photodissociation of jet-cooled CH3OH and C2HsOH was studied using the high-n Rydberg atom time-of-flight （TOF） technique. TOF spectra of nascent H atom products were measured. Simulation of these spectra reveals three different atomic H loss processes： one from hydroxyl H elimination, one from methyl （ethyl） H elimination, and one from secondary dissociation of the methoxy （ethoxy） radical. The relative branching ratio indicates secondary dissociation of ethoxy is less important than that of methoxy. The average angular anisotropy parameter of methanol is negative （with β≈-0.3）, indicating the transition dipole moment is perpendicular to the C-O-H plane. The slightly more negative β value of ethanol （with β≈-0.4） implies that ethanol has a longer rotational period. These experimental results indicate that both systems undergo fast internal conversion to the 3s surface after it is excited to the 3px surface, and then dissociate on the 3s surface. The translational energy distribution of the CH3O＋H products reveals extensive CH3 rocking or CH3 umbrella excitation in the CH30 radical. However the vibrational structures are not resolved in the C2H5O radical.

Ion-Velocity Map Imaging Study of Photodissociation Dynamics of Acetaldehyde

The photodissociation dynamics of acetaldehyde in the radical channel CH3＋HCO has been reinvestigated using time-sliced velocity map imaging technique in the photolysis wavelength range of 275-321 nm. The CH3 fragments have been probed via （2＋1） resonance-enhanced multiphoton ionization. Images are measured for CH3 formed in the ground and excited states （v2=0 and 1） of the umbrella vibrational mode. For acetaldehyde dissociation on T1 state after intersystem crossing from S1 state, the products are formed with high translational energy release and low internal excitation. The rotational and vibrational energy of both fragments increases with increasing photodissociation energy. The triplet barrier height is estimated at 3.8814-0.006 eV above the ground state of acetaldehyde.

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.

Ultraviolet Photodissociation Dynamics of DNCO+hν→D+NCO: Two Competitive Pathways

Photodissociation dynamics of DNCO+hv→D+NCO at photolysis wavelengths between 200 and 235 nm have been studied using the D-atom Rydberg tagging time-of-flight technique. Product translational energy distributions and angular distributions have been determined. Nearly statistical distribution of the product translational energy with nearly isotropic angular distribution was observed at 210-235 nm, which may come from the predissociation pathway of internal conversion from S1 to S0 state followed by decomposition on S0 surface. At shorter photolysis wavelengths, in addition to the statistical distribution, another feature with anisotropic angular distribution appears at high translational energy region, which can be attributed to direct dissociation on S1 surface. Compared with HNCO, the direct dissociation pathway for DNCO photodissociation opens at higher excitation energy. According to our assignment of the NCO internal energy distribution, dominantly bending and a little stretching excited NCO was produced via both dissociation pathways.

Ultraviolet Photodissociation Dynamics of m-Bromofluorobenzene at around 240 nm

The photodissociation dynamics of m-brornofluorobenzene has been experimentally investi- gated at around 240 nrn using the DC-slice velocity map imaging technique. The kinetic energy release spectra and the recoiling angular distributions of fragmented Br（2P3/2） and Br（2P1/2） atoms from photodissociation of m-bromofluorobenzene have been measured at diff）rent photolysis wavelengths around 240 nm. The experimental results indicate that two dissociation pathways via （pre-）dissociation of the two low-lying 1ππ excited states dominate the production process of the ground state Br（2P3/2） atoms. Because of the weak spin-orbit coupling eff）ct among the low-lying triplet and singlet states, the spin-orbit excited Br（2P1/2） atoms are mainly produced via singlet-triplet state coupling in the dissociation step. The similarity between the present results and that recently reported for o-bromofluorobenzene indicates that the substitution position of the fluorine atom does not significantly affect the UV photodissociation dynamics of bromofluorobenzenes.

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.

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.

Probing Wave Packet Dynamics of I2^- Anions with Pump-Probe Femtosecond Spectroscopy

The wave packet dynamics of I2^- anions is studied by using the time-dependent wave packet method. Two conclusions can be drawn from the calculations. First, the period of the total photoelectron signal oscillating with the propagation of delay time is about 750fs. Second, the photoionization of I2^- anions begin at the time 600 fs, and the time needed for the population of the electronic state of I2 neutral molecule to reach the maximum becomes shorter with the increasing delay time.

EOM-CCSD-Based Neural Network Diabatic Potential Energy Matrix for ^(1)πσ^(*)-Mediated Photodissociation of Thiophenol

A new diabatic potential energy matrix(PEM)of the coupled~^(1)ππ^(*)and~1πσ*states for the~1πσ*-mediated photodissociation of thiophenol was constructed using a neural network(NN)approach.The diabatization of the PEM was specifically achieved by our recent method[Chin.J.Chem.Phys.34,825(2021)],which was based on adiabatic energies without the associated costly derivative couplings.The equation of motion coupled cluster with single and double excitations(EOM-CCSD)method was employed to compute adiabatic energies of two excited states in this work due to its high accuracy,simplicity,and efficiency.The PEM includes three dimensionalities,namely the S-H stretch,C-S-H bend,and C-C-S-H torsional coordinates.The root mean square errors of the NN fitting for the S1 and S2 states are 0.89 and 1.33 me V,respectively,suggesting the high accuracy of the NN method as expected.The calculated lifetimes of the S1 vibronic 00 and31 states are found to be in reasonably good agreement with available theoretical and experimental results,which validates the new EOM-CCSD-based PEM fitted by the NN approach.The combination of the diabatization scheme solely based on the adiabatic energies and the use of EOM-CCSD method makes the construction of reliable diabatic PEM quite simple and efficient.

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.