Yujie Zhao

Photoionization and dissociation of the monoterpene limonene: mass spectrometric and computational investigation

The photoionization of the monoterpene limonene has been studied using tunable vacuum ultraviolet synchrotron radiation in the region from the threshold for ionization of the parent molecule up to 15.5 eV. The adiabatic ionization energy of limonene is derived from photoionization efficiency spectrum and found to be 8.27 eV, compared with the density functional theory calculations which yields a value of 8.08 eV (B3LYP/6-311++G). Primary dissociation pathways of the parent molecule ions are investigated by experimental observations and theoretical calculations. Most of the fragmentation channels occur via a rearrangement reaction prior to dissociation. Transition structures and intermediates for those isomerization processes are also determined.

Photofragmentation of Isoleucine by Vacuum Ultraviolet Photoionization

Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investigated with synchrotron radiation photoionization mass spectroscopy and theoretical calculations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions C5H12N+ (m/z=86), C2H5NO2+ (m/z=75), C5H9+ (m/z=69), C4H9+ (m/z=57), and CH4N+ (m/z=30) are determined to be 8.84±0.07, 9.25±0.06, 10.20±0.12, 9.25±0.10, and 11.05±0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31++G(d, p) levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.

Observation of mass analyzed threshold ionization using synchrotron radiation on a new-style time of flight mass spectrometer

We have developed an efficient and applicable apparatus that combines mass-analyzed threshold ionization (MATI) with continuous molecular-beam mass spectrometry using tunable vacuum ultraviolet synchrotron radiation at National Synchrotron Radiation Laboratory. The new design, in which the spoiling field and the pulsed ionization field are perpendicular to each other, can obtain efficiently the ionic spectra of molecule. The MATI spectra of Ar and N(2) have been recorded in the energy region between 15.5 and 17.5 eV to illustrate the feasibility of this scheme. With its unique features, the important experiment considerations are potentially a powerful tool for study of information of ionization energies and ionic states of complex organic compounds.

Synchrotron radiation VUV double photoionization of some small molecules

The VUV double photoionizations of small molecules (NO, CO, CO2, CS2, OSC and NH3) were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules were determined with photoionization efficiency spectroscopy. The total energies of these molecules and their parent dications (NO2+, CO2+, CO2+2, CS2+2, OSC2+ and NH2+3) were calculated using the Gaussian 03 program and Gaussian 2 calculations. Then, the adiabatic double ionization energies of the molecules were predicated by using high accuracy energy mode. The experimental double ionization energies of these small molecules were all in reasonable agreement with their respective calculated adiabatic double ionization energies. The mechanisms of double photoionization of these molecules were discussed based on a comparison of our experimental results with those predicted theoretically. The equilibrium geometries and harmonic vibrational frequencies of molecules and their parent dications were calculated by using the MP2 (full) method. The differences in configurations between these molecules and their parent dications were also discussed on the basis of theoretical calculations.

Dissociative photoionization of β-pinene: an experimental and theoretical study

We investigated the photoionization and dissociation photoionization of the β-pinene molecular using time-of-flight mass spectrometry with a tunable vacuum ultraviolet source in the region from 8.00 eV to 15.50 eV. The experimental ionization energy (IE) value is 8.60 eV using electron impact as the ionization source, which is not in good agreement with theoretical value (8.41 eV) with a G3MP2 method. We obtained the accurate IE of β-pinene (8.45 ± 0.03 eV) derived from the efficiency spectrum, which is in good agreement with the theoretical value (8.38 eV) of the CBS-QB3 method. We elucidated the dissociation pathways of primary fragment ions from the β-pinene cation on the basis of experimental observations in combination with theoretical calculations. Most of the dissociation pathways occur via a rearrangement reaction prior to dissociation. We also determined the structures of the transition states and intermediates for those isomerization processes.