Probing Ultrafast Dissociation Dynamics of Chloroiodomethane in the B Band by Time-Resolved Mass Spectrometry

Ultrafast dissociation dynamics of chloroiodomethane （CH2ICl） in the B band is studied by femtosecond time- resolved time-of-flight （TOF） mass spectrometry. Time-resolved TOF mass signal of parent ion （CH2ICl＋） and main daughter ion （CH2Cl＋） are obtained. The curve for the transient signal of CH2ICl＋ is simple and can be well fitted by an exponential decay convoluted with a Gaussian function. The decay constant determined to be less than 35 fs reflects the lifetime of the B band. Significant substituent effects on photodissociation dynamics of CH2IC1 compared with CH3I are discussed. The dissociation time from the parent ion CH2IC1＋ to the daughter ion CH2Cl＋ is determined in the experiment. The optimized geometry of the ionic state of CH2ICl and the ionization energy are calculated for further analysis of the measurements. In addition, compared with the parent ion, a new decay component with time constant of -596 fs is observed for CH2Cl＋, and reasonable mechanisms are proposed for the explanation.

Dissociation Dynamics of Nitrous Oxide from Jet-cooling Absorption Spectrum in 142.5-147.5 nm

The absorption spectrum of the C1Ⅱ state of N2O molecule in the wavelength range of 142.5-147.5 nm has been measured under the jet-cooled condition, and the clear spectral features are displayed. A vibrational progression is observed with a frequency interval of about 500 cm-1. With the aid of potential energy surfaces （PES） of the low-lying electronic states of N2O, the vibrational progression is assigned as the bending mode of the repulsive C1Ⅱ state. From the Fourier transformation analysis, the recurrence period of the periodic orbit near the transition state region is derived to be 65 fs. Through the least-square Lorentzian fitting, the lifetimes of the resonance levels are estimated from their profile widths to be about 20 fs, which is shorter than the recurrence period. Therefore, a new explanation is suggested for the observed diffuse spectral structure, based on the behavior of dissociating N20 on PES of the C1Ⅱ state in the present excitation energy range.

Theoretical Study of Haloacetonitrile Anions： CH2XCN^- （X=F, Cl）

Haloacetonitrile anions CH2XCN- （X=F, Cl） were studied by HF-SCF, Becke3-LYP, and MP2 methods together with the Dunning＇s basis set aug-cc-PVTZ. The vertical electron attachments to the neutral are endothermic. The geometrically optimized CH2FCN^- is mainly a valence-bounded anion and CH2FCN→CH2CN＋F^- is a nonadiabatic dissociation. This theoretical study in good agreement with the experimental results shows that the Becke3-LYP method is reasonable in describing the electronic structures of anions and dissociative attachment dynamics, while significant differences between MP2 and Becke3-LYP results are shown for the dissociation potential curves of CH2ClCN→CH2CN＋Cl^-.

Ultrafast Coulomb explosion imaging of molecules and molecular clusters

Taking an image of their structure and a movie of their dynamics of small quantum systems have always been a dream of physicists and chemists. Laser-induced Coulomb explosion imaging(CEI) provides a great opportunity to make this dream a reality for small molecules or their aggregation — clusters. The method is unique for identifying the atomic locations with angstrom spatial resolution and capturing the structural evolution with a femtosecond time scale, in particular for imaging transient state products. This review summarizes the determination of three-dimensional equilibrium geometry of molecules and molecular cluster system through the reconstruction from the fragments momenta, and also shows that the dissociation dynamics on the complex potential energy surface can be tracked in real-time with the ultrafast CEI(UCEI).Furthermore, the detailed measurement and analysis procedures of the CEI, theoretical methods, exemplary results, and future perspectives of the technique are described.

Production of cold CN molecules by photodissociating ICN precursors in brute-force field

We theoretically investigate the production of cold CN molecules by photodissociating ICN precursors in a brute-force field. The energy shifts and adiabatic orientation of the rotational ICN precursors are first investigated as a function of the external field strength. The dynamical photofragmentation of ICN precursors is numerically simulated for cases with and without orienting field. The CN products are compared in terms of their velocity distributions. A small portion of the CN fragments are recoiled to near zero speed in the lab frame by appropriately selecting the photo energy for dissociation. With a precursor ICN molecular beam of - 1.5 K in rotational temperature, the production of low speed CN fragments can be improved by more than 5 times when an orienting electrical field of 100 k V/cm is present. The corresponding production rate for decelerated fragments with speeds ≤ 50 m/s is simulated to be about ～2.1×10^-4 and CN number densities of 10^8 –10^10 cm^-3 can be reached with precursor ICN densities of ～10^12 –10^14 cm^-3 from supersonic expansion.