Adv. Studies Theor. Phys., Vol. 5, 2011, no. 1, 31 - 43 De-Excitation Auger Cascade Following InnerShell Ionization in Ne, Mg Atoms and Fe14+ Ions Y. A. Lotfy*, Adel M. Mohammedein-ElShemi, Adel A. Ghoneim Applied Sciences Department, College of Technological Studies P.O. Box 42325, Shuwaikh 70654, Kuwait [email protected], [email protected] *El-Minia University, Faculty of Science, Physics Department 61111 El-Minia, Egypt Abstract An inner-shell ionized atom relaxes via parallel radiative (x-ray) and nonradiative (Auger) transitions. The de-excitation decay of inner-shell vacancies gives rise to Auger spectra and yields highly charged ions. The successive radiative and Auger transitions lead to stable holes in the outer-shells of atoms. The radiative and non-radiative transition probabilities obtained using Dirac-Fock-Slater wavefunctions. The multiply charged ions yield after de-excitation decay of a hole in K and L1-subshell of Ne , Mg atoms and Fe14+ ion are calculated using Monte Carlo (MC) Simulation technique. The charged ions yield after K vacancy creation mainly turns into Ne2+ and Ne3+ ions. Doubly charged ions Ne+2 are predominate, whereas in L1 hole situation the singly charged Ne1+ ions are manly. At K hole states in Mg atoms, the yield of Mg3+ ions are predominate. The highest intensities are Fe16+ions in the K and L1 shell ionization. The average charged ions result after K and L1 vacancy production are calculated for Ne, Mg atoms and Fe14+ ions. The present results of charge state distributions of ions agree well with the experimental and theoretical data. Keywords: Ionization processes, Auger cascades, Multiply charged ions 1. Introduction Photoelectron emission lead to formation of core holes in atoms. These Core holes are eliminated by relaxation that is accompanied by: (1) X-ray fluorescence (Xray fluorescence spectroscopy) (2) Auger electron emission (Auger electron 32 Y. A. Lotfy, A. M. Mohammedein-ElShemi, A. A. Ghoneim spectroscopy). Atomic reorganization starts by filling the initially inner-shell vacancy by a radiative transition (x-ray) or by a non-radiative transition (Auger and Coster- Kronig processes). New vacancies created during this atomic reorganization may in turn be filled by further radiative and non-radiative transitions until all vacancies reach the outermost occupied shells (energetically stable final states or metastable ones because of relevant selection rules). In the case of x-ray processes the vacancy moves to an outer shell under emission of characteristic x-rays, while for non-radiative transitions one electron from an outer shell fills up the inner-shell vacancy and another electron is ejected into continuum. With exception of the K and L shells in heavy atoms, the Auger processes are much more probable than x-rays. The production of inner-shell vacancy in an atom and the de-excitation decays through radiative and non-radiative transitions due to a change of the atomic potential, this change leads to an additional electrons can be emitted to a continuum (electron shake off processes). In each Auger processes an electron ejects into continuum, a series of such events called vacancy cascade, gives rise to a highly charged ions. The charge state distributions of ions result from de-excitation decay on innershell vacancies were studied both experimentally and theoretically. The multiply charged ions following vacancy cascades in rare gas atoms were measured at some restricted energies of photos that could be obtained from the x-ray tubes, and the produced ions were analyzed with a magnetic spectrometer [1-5]. The charge state distribution of ions as a function of photon energies were measured by sweeping the photon energy across the ionization threshold [6-12]. The initial inner-shell vacancy produced by synchrotron radiation and the yield ions are analyzed by using the timeof flight mass spectrometer. There are tow major approaches to calculate the vacancy cascades and multiply charged ions following inner-shell vacancy production in atoms. The first method is based on straightforward construction of the de-excitation decay trees for radiative and non-radiative transitions [13-16]. The second method is based on simulation of all possible radiative and non-radiative pathways to fill the inner- shell vacancies in atoms [17-21]. Inner-shell ionization processes were analyzed under different points of view. Thereby, basic investigations of atomic properties as well as investigation in connection with other disciplines as solid state physics, plasmaphysics and astrophysics were of interest. Here the atomic reorganization cascades following inner-shell vacancy production and the creation of multiply ionized atoms connected with it. The importance of this process is based on the fact, which because of atomic reorganization cascades ionized atoms with different ion charge states are produced, e.g. as result of a primary inner-shell vacancy ions with different charge states can be created. In the present work, the charge state distribution of ions and the average ion charge, which produced from de-excitation decay of vacancies after K shell ionization in atoms, is calculated using Monte Carlo (MC) simulation technique. The Monte Carlo (MC) algorithms are applied to simulate all possible pathways of radiative and non-radiative transitions to fill the K- shell vacancy in these atoms. The radiative transitions of single ionized atoms are calculated using De-excitation Auger cascade following inner-shell ionization 33 mulitconfiguration Dirac Fock (MCDF) wave functions from Grant et al. [22]. The non-radiative transitions for single are calculated by using Dirac Fock Slater by computer code written by Lorenz and Hartmann [23]. The electron shake off processes which due to from the change of atomic potential after inner shell vacancy production and non-radiative transitions are calculated with an code given by ElShemi [24]. The results of final charge state distributions and average number of electrons are compared with available theoretical and experimental data. 2. Method of Calculation The description of the de-excitation vacancy cascades resulting from inner – shell ionization in an atoms and ground state ions is given in detail elsewhere Abdullah et al. [21]. Therefore, only a brief description of it is given in this section. The calculation technique is used for simulating de-excitation cascades decays following inner-shell vacancy creation, considering fluorescence yields ( radiative branching ratios), Auger and Coster- Kronig yields ( non- radiative branching ratios), and electron shake off processes. The radiative branching ratio is defined as the probability that the vacancy in an atom is filled through a x-ray transitions (photon emission), that is therefore given by A (i → f ) ω ( f → i) = r (1) Γ and Auger yield (non-radiative branching ratios), is the probability that the vacancy filled through Auger or Coster-Kronig transitions, A (i → f ) a( f → i) = a (2) Γ where Γ is the sum of the total radiative width Γ R and non-radiative width Γ A .The relationship between fluorescence yield ω and Auger yield a must hold ω + a =1 (3) The calculation of radiative transition rates were performed for single ionized atoms using Multiconfiguration Dirac Fock (MCDF) wave functions [22]. The nonradiative transition rates were computed with a code written by Lorenz and Hertmann [23] using Dirac Fock Slater (DFS) wave functions. The electron shake of process, that due to from a sudden change of atomic potential during vacancy cascade development, which can lead to the ejection of additional electrons through monopole processes, that are calculated using own code [24]. In this way we calculate the electron shake off probabilities according Åberg [25] by overlapping integrals between the wave functions of initial state ϕ i and the final state ϕ f of the considered process. The probability of an electron transition from the orbital nlj to the orbital n′l ′j ′ is given by p nlj →n′l ′j′ = ∫ϕ ∗ nlj ( A0 )ϕ n′l′j′ ( A)dτ 2 (4) 34 Y. A. Lotfy, A. M. Mohammedein-ElShemi, A. A. Ghoneim with ϕ nlj ( A) and ϕ n′l′j′ ( A0 ) being orbital wave functions for the orbital nlj and for the orbital n′l ′j ′ in the ion A0. Thereby the ion originates from the atom A during a change in the potential in the course of the ionization processes. The probability that at least one of N electrons located in the sub-shell nlj becomes ionized is given by 2 ∗ p = 1- ( ∫ ϕ nlj ( A0 )ϕ n′l′j′ ( A)dτ )N – pf (5) where the quantity pf represented a correction for physically not allowed transitions to occupied shells and has the form 2 N′ ∗ pf = ∑ N ϕ ( A ) ϕ ( A ) d τ (6) ′ n lj nlj 0 2 j +1 ∫ n′lj with n′ ≠ n and N ′ as number of the electrons in the orbital n′lj . The calculation technique is based on the simulating of the de-excitation vacancy cascade originating from a configuration with a single vacancy. Each cascade starts with the implementation of atomic data for all possible x-ray , Auger, Coster Kronig, and shake off channels. To realize a Monte Carlo selection of the actual de-excitation channel, the probabilities of all de-excitation channels were normalized to one. Let N denote the number of vacancies created in nl subshells of an atomic configurations via radiative or non-radiative transitions. For example , The configuration 1s 2s2 2p6 3s2 3p6 would represent a distribution with a single K-shell vacancy (N=1);1s2 2s2 [2p5] 3s2 [3p5] would represent a distribution that could be formed via an Coster-Kronig transition. Electron symbol in the square brackets will be used to indicate spectator holes. After creating a new spectator vacancy in an actual configuration, the program at first controls whether shake-off takes place or not. If the random number generated is smaller than the sum of all normalized shake off probabilities of the preceding vacancy configuration, then a shake-off process tacks place, i.e. an additional electron ejected in an higher subshell. The channel whose subshell shake –off probability value coincides with the random number generated will be activated. After the decision about the occurrence of shake –off processes the program selects the following de-excitation trees by generating a new random number. Here at first a comparison of the value of random number and the fluorescence yield proves whether radiative or non-radiative take place. The actual de-excitation channel after this decision is chosen in analogy with the determination of the shake-off channels. Each new configuration is analyzed to see if further decay are possible, If they are, then the program code goes back to the first step described above. The generation of new vacancy configurations continues until all vacancies have reached the outer shells or no further decays are possible. If no further decays are possible for any of the final configurations we have a complex de-excitation tree ending up with a great number of configurations each of which is characterized by its probability depending on its de-excitation history. The charge state degree of ions ( Z f ) in outer shells are recorded. After finishing the de-excitation tree the same inner shell vacancy will be simulated again. The probabilities of charged ions state De-excitation Auger cascade following inner-shell ionization distributions p ( Z f ) and the average charged ions Zf 35 are recorded after 105 histories. 105 p(Z f ) = ∑Z i f 1 n here the subscript i is denoted to the equal produced ionization degree for Z f and n the histories ( =105 ) in our calculation. The mean charge state of ions is given by Z f = ∑ p( Z if ) Z if (7) (8) The change of radiative (x-ray photon ) and non- radiative (Auger and Coater – Kronig ) transition rates is considered in the present work. This change aris from the photons and electrons emission in course of atomic rearrangement following inner – shell vacancy,. The calculation of transition rates for intermediate configuration with spectator vacancies during the cascade propagation is based on the radiative and non-radiative transition rates for single ionized atom Jacobs et al. [26]. The radiative transition rates (x- ray transition) are given by a r ( n1l1N1 , n 2l 2 N 2 → n1l1N1 −1 , n 2l 2 N 2 +1 ) = N1 ( 4l2 + 2 − N 2 ) A r ( n1l1 → n 2l 2 ) ( 4l 2 + 2) (9) and the non-radiative transition rates are N N a a (n1l1 1 , n3 l3 3 , n 4 l 4 N1 N4 → n1l1 N1 −1 , n3 l 3 N 3 +1 , n4 l 4 N 4 +1 )= (4l 3 + 2 − N 3 ) (4l 4 + 2 − N 4 ) Aa (n1l1 → n3l 3 , n 4 l 4 ) (4l 3 + 2) (4l 4 + 2) N a a (n1l1 1 , n3l3 N3 → n1l1 N1 −1 , n3 l 3 N3 + 2 (10) )= (11) N1 (4l3 + 2 − N 3 ) (4l3 + 1 − N 3 ) 2 Aa (n1l1 → n3l3 ) 2 (4l3 + 2) (4l3 + 1) where Ar and Aa are the radiative and non-radiative transition rates for single ionized atom, respectively. ar and aa are the transition rates for atom with various spectator inner shell vacancies. n1l1 is initial state and n3l3 ,n4l4 are a final state in equation (10) (e.g. K-LM transition ), but in equation (11) the n3l3 is the final state such as ( K → MM transition).Ni is the number of vacancies in the nili sub-shell. Because most Coster–Kronig energies are so low and the rates are so sensitive to the transition energy, so some Coster–Kronig channels may be energetically forbidden during the cascade de-excitation decays. The production of various vacancies in intermediate configurations during the cascade decay due to a closing of Coster - Kronig channels. This effect well be considered in our treatment by using a semi empirical approaches so-called “ Z+1 rule”, which specifies that the effect of the nl vacancy on the binding energy of the n'l ' electron can be 36 Y. A. Lotfy, A. M. Mohammedein-ElShemi, A. A. Ghoneim approximated by taking the n'l ' binding energy in the neutral atom of next –higher atomic number Then the kinetic energy E∞l A of the continuum electron emitted in a radiationless transition is given by E∞l A = En ''l '' − 1 [ Enl ( Z ) + Enl ( Z + 1) + En 'l ' ( Z ) + En 'l ' ( Z + 1)] 2 (12) Where En ''l '' , and Enl ( Z ) are the absolute value of neutral atom binding energies, while Enl ( Z + 1) and En 'l ' ( Z + 1) are the binding energies of the next higher atomic number. However, Auger and Coster – Kronig transitions are energetically impossible if En ''l '' p 1 [ Enl ( Z ) + Enl ( Z + 1) + En 'l ' ( Z ) + Enl ( Z + 1)] 2 (13) If Coster–Kronig transitions are energetically possible, they tend to provide the dominant channel for inner shell vacancy decay in an atom or ion. 3. Results and discussion The branching ratios (%) to individual channels for all possible transitions state configurations resulting after K-shell vacancy creation in neutral Ne and Mg atoms are listed in Tables 1. The fluoresce yields of 4.34% and 2.16% belong to the x-ray K-L23 transitions for Ne and Mg, respectively. The radiative channels (x-ray transitions) are generally much weaker than the non-radiative channels (Auger transitions) for K-shell vacancy decay in neon and magnesium. Therefore, the probability of formation ion charge through x-ray transitions in Ne and Mg are low. For Auger channels in Ne, the dominant transitions are correspond to K-L1L1, KL1L23, and K-L23L23 with Auger yields 19.62%, 28.05% and 48.14% respectively. From the Auger yields of the previous transitions for Ne atom, it is obvious, that the K-L23L23 is the strongest one and the second one is K-L1L23 transition. Therefore, the probability of filling the K- shell vacancy through these Auger channels is extremely high. The decay of inner shell vacancy in neon through Auger transitions leads to double ion charge. The treble charged ions are due to from Auger channels and shake-off processes. The branching ratio for K- L1L1, -L1L23 and – L23L23 transitions in Mg atom are 14.2%, 36.90% and 35.21% respectively. The branching ratio for KLM transitions are approximately 11.5%. The filling of inner shell hole in Mg through Auger transitions K-LL leads to highly charged ions Mgn+ (n ≥ 2 ). The total Auger yield after K-shell vacancy production for Ne and Mg are approximately 96% and 98%, respectively. 37 De-excitation Auger cascade following inner-shell ionization Final states (Ne) Branching ratio (%) Final states (Mg) L23 L1L1 L1L23 L 23L23 4.34 19.62 28.05 48.14 Total radiative yield 4,34 95.81 L23 L1L1 L1L23 L1M1 L 23L23 L23M1 M1M1 Total radiative yield Total Auger yield Total Auger yield Branchin g ratio (%) 2.16 14.2 36.90 10.24 35.21 1.23 0.05 2.16 97.84 Table1: Branching ratios (%) for the decays of Ne and Mg after K- shell electron ionization. Fig. 1a shows the results of Nei+ ions following de-excitation decay after Kshell vacancy in Ne atom. The results obtained by performing the calculation with considering the electron shake off processes. The results for charge state distributions with consideration electron shake off probability demonstrates the importance of this process in the calculation of vacancy cascades in atoms. The calculation of charge state distributions with consideration of shake off process agree well with experimental value. The de-excitation of a primary K -shell vacancy in neon occurs with high probability by 1s2- 2s22p4 Auger transitions because of the small K fluorescence yield (ω (Ne) = 0.04) and Auger yield is (a =0.96). As a result of this KLL Auger transitions the contribution of Ne2+ ions is 79 %. New vacancies created by this process could not further de-excite by non-radiative electron transitions. The triple Ne3+ ions are produced by contribution of Auger and shake off processes. From this situation, the production of vacancies in the outermost subshells occurs from shake off processes, if non-radiative de-excitation transitions are impossible. The contribution of Ne3+ ions in the charge state distribution (CSD) are approximately 17%. The highest final charge state from K shell hole is found to be Ne2+ ions. The average charged ions <Zf> = 2.11. The charge state distributions (CSD) following vacancy production in L1 subshell are presented in Figure 1b. The contribution of Auger process after L1 hole creation is not possible. Therefore the Ne1+ (L1) is strongest, because no de-excitation decays following L1 vacancy production in Ne atoms. The consideration of shake process is due to formation of Ne2+ ions. The result of double ionization Ne2+ is small. The mean charged ions <Zf> = 1.88. As shown from the Fig., the results agree well with the experiment data. 38 Y. A. Lotfy, A. M. Mohammedein-ElShemi, A. A. Ghoneim 1 Present work Kochur [14 ] Omar and Hahn[15] Exp [2] a 0.8 Probability Ne (K+1), <Z>=2.11 0.6 0.4 0.2 0 0 1 2 3 Ion charge 4 5 1 Present work Exp [2] b 0.8 Probability Ne(L1-1) , <Zf>=1.1 0.6 0.4 0.2 0 0 1 2 3 Ion charge 4 5 Fig. 1. The charge state distributions (CSD) with consideration of shake off process in Ne atom after vacancy creation in K and L1 shells production The charge state distributions following K- and L1- subshell vacancies deexcitation in Mg and another available theoretical values [15,20] are compared in figure 2a,b. The Mg(K1+) ionization mainly produces Mg2+, Mg3+ and Mg4+ ions, the doubly Mg2+ and triply Mg3+ charged ions appeared strongly in the distribution. The spectrum of the number of ejected electrons after K- shell vacancy de-excitation forms an asymmetric peak. The probabilities of charge states are decreasing at lower and higher end of the distributions, and the maximum probable charge states appear in the middle distribution as shown in Fig.2a. The mean charge state of ions <Zf> = 39 De-excitation Auger cascade following inner-shell ionization 2.9. The final charge state distributions following L1 hole production in Mg are shown in Fig.2b. The doubly Mg2+ ions appeared strongly in the charge state distributions (CSD). The formation of Mg3+ results from the contribution of L-LM and L-MM Auger channels and shakes process. The average charge state of ions <Z> after L1 hole creation is equal to 2.2. 1 Present work Omar and Hahn [15] Opendak[ 20 ] a 0.8 Probability Mg(K-1), <Zf>=2.9 0.6 0.4 0.2 0 0 1 2 3 4 Ion charge 5 6 7 1 Present work Omar and Hahn [15] Opendak[20] b 0.8 Probability Mg(L1-1), <Zf>=2.2 0.6 0.4 0.2 0 0 1 2 3 4 Ion charge 5 6 7 Fig.2: The charge state distributions (CSD) with consideration of shake off process in Mg atom after vacancy creation in K and L1 shells production Fig.3a,b shows the probability of final charge state distributions for Fe14+ ions after de-excitation of K and L1 vacancy. The calculated results are compared with 40 Y. A. Lotfy, A. M. Mohammedein-ElShemi, A. A. Ghoneim other calculations. The ionization in the K shell induces the multiply charged ions from Fe15+ to Fe16+ ions. The probabilities of charge states are decreasing at lower and higher end of the distributions, and the maximum probable charge states appear in the middle distribution as shown in Fig.3a. The Fe16+ ions appeared strongly in the charge state distributions (CSD) after K and L1 shell vacancies as appear in Fig. 3a,b. The mean charge state of ions <Zf> = 2.11 for K ionization and <Zf >= 1.88 for L1 ionization, respectively. 1 Present work Omar and Hahn[15] Opendak [20] a 0.8 Probability Fe14+(K-1), <Zf>=2.11 0.6 0.4 0.2 0 13 14 15 16 17 Ion charge 1 18 19 Present work Omar and Hahn [15] Opendak [20] b 0.8 Probability Fe14+(L1-1), <Zf>=1.88 0.6 0.4 0.2 0 13 14 15 16 17 Ion charge 18 19 Fig. 3. The charge state distributions (CSD) with consideration of shake off process in Fe14+ ion after vacancy creation in K and L1 shells production De-excitation Auger cascade following inner-shell ionization 41 4. CONCLUSIONS The ion charge state distribution (CSD) of single ionized Ne1+, Mg1+ atoms and Fe ion are computed using Monte Carlo (MC) simulation technique. All allowed radiative, non-radiative branching ratios and electron shake off probabilities are taken into account in the calculation of relative abundances of charged ions. Multiconfiguration Dirac Fock Slater (MDFS) wave functions are applied to calculate radiative (x-ray) transitions. The Auger transition rates and electron shakeoff probabilities are obtained using Dirac-Fock-Slater wavefunctions. At K hole states in Ne and Mg atoms, the yield of Ne2+ and Mg3+ ions are predominate, respectively. The highest intensities are Fe16+ions in the K and L1 shell ionization. The present results of charge state distributions of ions agree well with the experimental and theoretical data. 14+ References [1] Carlson, T. A., Krause, M.O., 1965. Atomic readjustment to vacancies in the K and L shells of argon. Phys. Rev. 137, A1655-1662. 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