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Project supported by the National Natural Science Foundation of China (Grant Nos. 11327404 and U1432118) and the Natural Science Research Programme of Education Department of Anhui Province, China (Grant Nos. KJ2013A260 and KJ2016A749).
The relativistic and distorted wave effects are investigated for the electron momentum distributions of Xe 4d electrons. The theoretical results show good agreements with the experimental data measured previously with electron momentum spectroscopy. The distorted wave effect and the relativistic effect are found to play important roles in the low and high momentum regions, respectively.
Relativistic effects of high-Z atoms and molecules containing high-Z atoms have been attracting a great deal of research interest.[1–15] The relativistic effects can be divided into a direct relativistic effect and an indirect relativistic effect.[3] The direct relativistic effect includes kinematical and spin–orbit coupling effects. The kinematical one is caused by electrons moving with high speeds near the heavy nucleus, which results in the spatial contractions of orbits s and p and the energy loses. The spin–orbit (SO) coupling effect is a result of interaction between the electron’s spin magnetic and orbit moments, leading to the energy-level splitting. The indirect relativistic effect refers to the contraction caused by the inner orbit which can block the heavy nuclear more severely, leading to the outer orbits d and f expanding in the location space and improving the energy.
Photoelectron spectroscopy, nuclear magnetic resonance (NMR), and Compton scattering are the basic experimental methods to explore the relativistic effects. On the other hand, electron momentum spectroscopy (EMS) has its unique advantages in the study of the relativistic effects, which can show the relativistic effects not only on the ionization energies but also on the orbital wave functions of a heavy atom via the measurements of electron momentum distribution. This is particularly true for xenon, for which a significant number of electron momentum spectroscopy studies (Leung and Brion,[4] Cook et a1.,[5,6] Braidwood et al.,[7] Brunger et al.,[8] Brion et al.,[9] Ren et al.[10]) and photoelectron spectroscopy (PES) measurements (Gelius,[11] Svensson et al.,[12] Krause et al.[13]) have been carried out. The PES works of Gelius[11] and Svensson et a1.[12] have examined these core states in detail; the importance of these studies lies in their accurate determination of the binding energies of the 4d5/2 and 4d3/2 states.
In 1984, Cook et al.[5,6] for the first time studied the relativistic effects on the outermost layer of the Xe atom’s 5p orbital in view of the wave function by the EMS technique. Due to the poor energy resolution (∼ 1.6 eV) of their spectrometer, the SO splitting bands (with an energy spread ∼ 1.3 eV) about the ionization of Xe 5p orbital could not be resolved clearly; the electron momentum distributions and the branching ratio of two splitting components 5p3/2 and 5p1/2 were obtained by the spectral deconvolutions.[5,6] In 1994, Brunger et al.[8] reported the momentum distribution about Xe 4d electrons. Although they observed peak splitting (with an energy spread ∼ 1.97 eV) between 4d5/2 and 4d3/2 states, they did not find the difference of SO coupling effects on the electron momentum distributions of these two states. In 1998, Brion et al.[9] reported, using the EMS technique, the distorted wave effect on the low momentum distribution region of Xe 4d electrons, but they did not go into the details of the SO coupling effect. In 2006, using the EMS spectrometer with an energy spread of 1.2 eV, Ren et al. measured the electron momentum distributions of the SO splitting components 4d5/2 and 4d3/2 of Xe and found the variations of the branch ratio between these two components with the change of the incident electron energy (
In this paper, we calculate the wave function of Xe 4d5/2 and 4d3/2 with the relativistic density functional theory (RDFT), then obtain the electron momentum distributions of the two components of Xe 4d5/2 and 4d3/2 electrons and the branch ratios of the angular-resolved differential cross section. In comparison to the low region of the electron momentum distributions between the experimental[10] and theoretical results, the distorted wave Born approximation (DWBA) is used because of the well-known distorted wave effect on the 4d electron.
(e, 2e) as a single-collision ionization process can be studied with EMS, which is a kinematical complete measurement technique. Completely observed quantity of this reaction is a triple differential scattering cross section (TDCS), which is expressed in atomic unit as[16,17]
Under the distorted wave Born approximation (DWBA), the ionization amplitude is expressed as follows:[18]
When calculating the distorted wave with partial wave method, we adopt equivalent local central potential
In the case that the impact energy is larger (
For the heavy element atoms or molecules containing heavy elements, relativistic effects have an obvious impact on the wave function, we need to use the theory of relativity quantum chemical method to calculate it. The scalar relativistic (SR) method is used here for treating the relativistic effect on Xe 4d electrons. The theoretical calculations are performed with the density functional program ADF.[24,25] The B3LYP density functional and the relativity ZORT[26] / TZ2P basis set are adopted in the calculations. The distorted wave effect is considered by using the distorted wave program with the DWBA method[27] and the SR wave functions obtained in the above B3LYP calculations. Non-relativistic (NR) calculations based on Eq. (
The theoretical electron momentum distributions of Xe 4d5/2 and 4d3/2 are shown in Figs.
To further elucidate the distorted wave effect, in particular, in the low electron momentum region, the experimental momentum profiles by summation of two SO splitting components are compared with the NR and SR theoretical results in Fig.
The electron momentum distributions of Xe 4d electrons are investigated theoretically by considering the relativistic and distorted wave effects, and compared with the EMS experimental data recorded at different impact energies.[10] The distorted wave effect is significant in the low momentum regions of both spin–orbit splitting 4d5/2 and 4d3/2 ionization states, while the relativistic effect is remarkable in the high momentum regions.
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[4] | |
[5] | |
[6] | |
[7] | |
[8] | |
[9] | |
[10] | |
[11] | |
[12] | |
[13] | |
[14] | |
[15] | |
[16] | |
[17] | |
[18] | |
[19] | |
[20] | |
[21] | |
[22] | |
[23] | |
[24] | |
[25] | |
[26] | |
[27] |