화학공학소재연구정보센터
Journal of Chemical Physics, Vol.100, No.2, 1011-1020, 1994
Nonoptical Excited-State Spectroscopy of Chf2Cl - Characterization of Nondipole N-)Sigma-Asterisk Valence Transitions by Angle-Resolved Electron-Energy-Loss Spectroscopy
A nondipole low-lying excitation feature at 8.0 eV in difluorochloromethane (CHF2Cl) has been observed in angle-resolved electron energy loss spectra obtained at 2.5 keV impact energy. Based on the results of a single-excitation configuration interaction calculation, we assign this feature predominantly as electronic transitions from Cl nonbonding 14a’ and 7a" orbitals [the highest occupied molecular orbital (HOMO) and second HOMO, respectively] to an antibonding sigma(C-Cl)* 15a’ orbital (the lowest unoccupied molecular orbital), the so-called n --> sigma* type transitions. The generalized oscillator strength (GOS) profile of this transition has been determined and found to be similar in shape and magnitude to that of a recently reported n(Cl) --> sigma(C-Cl)* (7e --> 11a1) transition in CF3Cl [Ying et al., Chem. Phys. Lett. 212, 289 (1993)]. Both GOS profiles are found to have a shape characteristic of a quadrupole transition, with a maximum at momentum transfer of approximately 1 a.u. The similarity in the nature of these n(cl) --> sigma(C-Cl) transitions in CHF2Cl and CF3Cl to that of a p-to-p transition in a chlorine atom can be demonstrated qualitatively by using contour maps of the density functions of the dominant initial-state and final-state orbitals generated from ab initio self-consistent field wave functions. The homology of transition-related properties (including the GOS profile) among the n(Cl) --> sigma(C-Cl)* transitions in "simple" polyatomic molecules that contain a single highly localized C-Cl bond is also discussed. Furthermore, the calculated potential energy diagram for CHF2Cl along the C-Cl bond direction suggests that electronic transitions from the 14a’ and 7a" orbitals to the 15a’ orbital may lead to dissociation of the C-Cl bond. Such predissociation may represent a possible common consequence of the n(Cl --> sigma(C-Cl)* transitions in these monochloro-substituted chlorofluorocarbons and related derivatives.