One-photon mass-analyzed threshold ionization spectroscopy of 2-chloropropene (2-C3H5Cl) and its vibrational assignment based on the density-functional theory calculations

Abstract

Articles you may be interested inOne-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure One-photon mass-analyzed threshold ionization spectroscopy of C H 2 Br I : Extensive bending progression, reduced steric effect, and spin-orbit effect in the cation J. Chem. Phys. 123, 024310 (2005); 10.1063/1.1954770 Vibrational assignment and Franck-Condon analysis of the mass-analyzed threshold ionization (MATI) spectrum of CH 2 ClI : The effect of strong spin-orbit interaction J. Chem. Phys. 122, 244319 (2005); 10.1063/1.1948384One-photon mass-analyzed threshold ionization spectroscopy of 1,3,5-trifluorobenzene: The Jahn-Teller effect and vibrational analysis for the molecular cation in the ground electronic state A high-quality mass-analyzed threshold ionization ͑MATI͒ spectrum of 2-chloropropene, 2-C 3 H 5 Cl, is reported. Its ionization energy determined for the first time from the 0-0 band position was 9.5395± 0.0006 eV. Almost all the peaks in the MATI spectrum could be vibrationally assigned utilizing the frequencies calculated at the B3LYP/ 6-311+ + G͑3df ,3pd͒ level and the Franck-Condon factors calculated with the molecular parameters obtained at the same level. In particular, the observed methyl torsional progression could be reproduced very well through quantum-mechanical calculations using the molecular parameters obtained at this level. Dramatic lowering of the torsional barrier inferred from the experimental data was entirely compatible with the B3LYP/ 6-311+ + G͑3df ,3pd͒ results. The torsional barrier and the internal rotational constant determined by fits to six torsional peaks were 53.6 and 5.20 cm −1 , respectively. A brief discussion at the level of molecular orbital is presented to account for the dramatic lowering of the torsional barrier upon ionization.

Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene

“…The BMK/6-311++G(3df,3pd) optimized structure is shown in the Figure . Previous reported values for the 2-chloropropene geometrical parameters at MP2/6-311G(d,p) and B3LYP/6-31G(d) levels from Parsons et al, B3LYP/6-311++G(3df,3pd) from Bae et al, and B3LYP/6-311++G(d,p) from Chang et al are in good agreement with the present results.…”

“…All values are in good agreement with previous theoretical results. 6,30,31 In addition, mode assignments obtained from the animation of the normal modes and by comparison with species containing similar chemical groups, are included in Tables 2 and B (Supporting Information). Certainly, some of the modes are strongly coupled, and therefore, only approximate assignments are given.…”

Multiphoton Dissociation and Ionization Dynamics of Allyl Chloride Using Femtosecond Laser Pulses

“…As a prototype of aliphatic halides, allyl chloride has attracted a great deal of interest due to its complex photodissociation dynamics [1][2][3][4][5][6][7][8][9][10][11][12][13] . The radiation of a UV photon possibly leads to C-Cl bond breaking and/or HCl elimination.…”

“…Both groups found that at least two channels are involved in the dissociation. As for the ionization dynamics, important constants, such as the accurate ionization potential, were also measured 11,12 .…”

Torsional vibrational structure of the propene radical cation studied by high-resolution photoelectron spectroscopy

“…[25][26][27] The questions concerning the relative stability of the eclipsed and staggered conformations of cations containing CH 3 -CH=X functionalities can now be answered experimentally. For instance, Kim and his co-workers 28,29 have exploited mass-analyzed thresholdionization spectroscopy to study the methyl-torsional motion in CH 3 -CX=CH + 2 (X=Cl, Br) and found that the eclipsed form [ Fig. 1(a)] is favored both in the neutral and the cation, but that the barrier is very strongly reduced (to ∼50-100 cm −1 ) in the cations compared to the neutrals (∼1000 cm −1 ).…”