Rapid internal conversion in a symmetric molecule LD 700 studied by means of femtosecond fluorescence depletion

The rapid internal conversion dynamics at room temperature is determined by using the femtosecond time-resolved fluorescence depletion measurements of a complex solvated molecule of LD 700 （rhodamine 700） combined with steadystate absorption and fluorescence spectroscopy, as well as quantum chemical calculation. The molecule is excited by a 50 fs laser pulse at 400 nm which directly populated the highly excited singlet state, the rapid internal conversions （ICs） are observed, which leads to the directional changes of the emission transition moment following photoexcitation to the highly excited singlet state S5 of LD 700.

Internal Conversion Process of Chlorophyll a in Solvents in Femtosecond Pump-Probe Laser Fields

The internal conversion （IC） processes of chlorophyll a （chl-a） in solvents are studied based on the reduced density matrix theory. The IC times can be obtained by simulating the experimental fluorescence depletion spectra （FDS）. The calculated IC times of chl-a in ethyl acetate, tetrahydrofuran and dimethyl formamide are 141, 147, and 241 fs, respectively. The oscillation feature of the FDS results from the forward and backward transfer of the population between coupled electronic states. The effects of diabatic coupling between two electronic states on the IC time and the FDS are described. The influence of molecule-reservoir coupling on the IC time is also investigated.

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.

Theoretical Study of the Photochemical Reaction Mechanism of Bicyclo[4.1.0]heptane

The photochemical reaction of bicyclo[4.1.0]heptane was studied at the complete active space SCF（CASSCF） level with a 6-31G^＊ basis set. A muhireference MP2 algorithm that has been implemented in the Gaussian program was used to correct the energetics for the dynamic correlation. Starting from the Franck-Condon excitation of bicyclo [ 4.1.0 ] heptane, the reaction is via two bonds＇ breakage to give rise to 1,6-heptdiene. One internal conversion （IC） and two intersystem crossing points（ISC） were located and are discussed separately. The reaction proceeds to its own characteristic product on the ground 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.

A semiclassical molecular dynamics of the photochromic ring-opening reaction of spiropyran

The photochromic ring-opening reaction of spiropyran（SP） has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF（12 10）/MS-CASPT2 potential energy curves（PECs） of S0–S2.The main simulation results show the dominate pathway corresponds to the ringopening process of trans-SP to form the most stable merocyanine（MC） product.These findings provide more important complementarity for interpreting experimental observations.

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.

Mini-orange spectrometer at CIAE

A mini-orange spectrometer used for in-beam measurements of internal conversion electrons, consisting of a Si（Li） detector and different sets of Sm05 permanent magnets for filtering and transporting the conversion electrons to the Si（Li） detector, has been developed at the China Institute of Atomic Energy. The working principles and configuration of the mini-orange spectrometer are described. The performance of the setup is illustrated by measured singles conversion electron spectra using the mini-orange spectrometer.