Vacuum Ultraviolet Photodissociation Dynamics of N_(2)O+hν→N_(2)(X^(1)Σg+)+O(^(1)S0) in the Short Wavelength Tail of D^(1)Σ+Band

Vacuum ultraviolet photodissociation dynamics of N2O+hν→N2(X^(1)Σg+)+O(^(1)S0)in the short wavelength tail of D^(1)Σ+band has been investigated using the time-sliced velocity-mapped ion imaging technique by probing the images of the O(^(1)S0)photoproducts at a set of photolysis wavelengths including 121.47 nm,122.17 nm,123.25 nm and 123.95 nm.The product total kinetic energy release distributions,vibrational state distributions of the N2(X^(1)Σg+)photofragments and angular anisotropy parameters have been obtained by analyzing the raw O(^(1)S0)images.It is noted that additional vibrationally excited photoproducts(3≤v≤8)with a Boltzmann-like feature start to appear except the non-statistical component as the photolysis wavelength decreases to 123.25 nm,and the corresponding populations become more pronounced with decreasing of the photolysis wavelength.Furthermore,the vibrational state specific anisotropy parameterβat each photolysis wavelength exhibits a drastic fluctuation nearβ=1.75 at v<8,and decreases to a minimum as the vibrational quantum number further increases.While the overall anisotropy parameterβfor the N2(X^(1)Σg+)+O(^(1)S0)channel presents a roughly monotonical increase from 1.63 at 121.47 nm to 1.95 at 123.95 nm.The experimental observations suggest that there is at least one fast nonadiabatic pathway from initially prepared D^(1)Σ+state to the dissociative state with bent geometry dominating to generate the additional vibrational structures at high photoexcitation energies.

High-resolution photofragment translational spectro- scopy for the UV photodissociation of C_2H_5I

The photodissociation of ethyl iodide at 279.71, 281.73, 304.02 and 304.67 nm has been studied on our new mini-photofragment translational spectrometer with a total flight path of only 5 cm. Some vibra-tional peaks are firstly resolved in the TOF spectra of I*(2P1/2) and I(2P3/2) channels. These vibrational peaks are assigned to the excitation states (ν2 = 0, 1, 2,…) of the umbrella mode (ν2, 540 cm-1) of the photofragment C2H5, and the distribution of the vibrational states is obtained. The dissociation energy has been determined to be D0(C-I)=2.314 ± 0.03 eV. The energy partitioning of the available energy (Eavl=ET+Eint=ET+EV,R) calculated from our experimental data E int /E avl= 22.1% at 281.73 nm, 22.4% at 304.02 nm for the I* channel, and E int /E avl= 25.2% at 279.71 nm, 25.9% at 304.67 nm for the I channel, seem to be more reliable.

Photodissociation of acryloyl chloride in the gas phase

The 193 nm photodissociation dynamics of CH2CHCOC1 in the gas phase has been examined with the technique of time-resolved Fourier transform infrared emission （TR-FTIR） spectroscopy. Vibrationally excited photofragments of CO （v ≤ 5）, HC1 （v ≤ 6）, and C2H2 were observed and two photodissociation channels, the C-C1 fission channel and the HC1 elimina- tion channel have been identified. The vibrational and rotational state distributions of the photofragments CO and HC1 have been acquired by analyzing their fully rotationally resolved v→ v- 1 rovibrational progressions in the emission spectra, from which it has been firmly established that the mechanism involves production of HC1 via the four-center molecular elimination of CH2CHCOC1 after its internal conversion from the S1 state to the So state. In addition to the dominant C--C1 bond fission along the excited S1 state, the S1→S0 internal conversion has also been found to play an important role in the gas phase photolysis of CH2CHCOC1 as manifested by the considerable yield of HC1.