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題名: Rotational States of an Adsorbed Dipole Molecule in an External Electric Field
作者: Shih, Yu-Tai;Liao, Y. Y.;Chuu, D. S.
貢獻者: 物理學系
日期: 2003-08
上傳時間: 2013-01-07T09:25:33Z
出版者: The American Physical Society
摘要: The rotational states of an adsorbed dipole molecule in an external electric field were investigated. The surface hindering potential was modeled as a finite conical well and a dipole-field interaction was added to the hindering potential. The molecular wave functions were expressed in terms of the eigenfunctions of molecular hindered rotation in the absence of electric field. Eigenenergies were determined by the matrix diagonalization procedures. Our results showed that, for both vertically and horizontally adsorbed molecules, there is avoided crossing between two adjacent rotational energy levels, as the field strength is increased, and finally all state energies decrease rapidly as the field strength is strong enough. The avoided crossing is due to the redistribution of wave function between different potential well regions. By employing the sudden unhindrance approximation, the rotational-state distributions of molecules desorbing from a solid surface in the presence of external electric field were calculated. Our results showed that the rotational-state distributions are significantly influenced by the external electric field. Since the electric field increases the ground-state energy of adsorbed molecule, the distribution shifts towards the high-J region if the electric field is applied to orient the molecular axis against the molecular preferred orientation. On the contrary, the distribution shifts towards the low-J region if the electric field is applied to orient the molecular axis towards molecular preferred orientation because the electric field decreases the ground-state energy of adsorbed molecule. The solutions to the finite conical well were also used to calculate the rotational alignment in the photodesorption of CO from Cr2O3(0001). Our results showed that at low-J values the CO molecules desorb like a helicopter, while at high-J values a cartwheel-like motion is preferred. This result is in qualitative agreement with the experimental observation.
關聯: Phys. Rev. B, 68(7): 075402-1-075402-10
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