Relative K X-ray intensity ratios of the first and second transition elements in the magnetic field

Journal Pre-proof Relative K X-ray Intensity Ratios of The First and Second Transition Elements in The Magnetic Field

Mine UĞURLU, Lütfü DEMİR PII:

S0022-2860(19)31567-4

DOI:

https://doi.org/10.1016/j.molstruc.2019.127458

Reference:

MOLSTR 127458

To appear in:

Journal of Molecular Structure

Received Date:

07 October 2019

Accepted Date:

20 November 2019

Please cite this article as: Mine UĞURLU, Lütfü DEMİR, Relative K X-ray Intensity Ratios of The First and Second Transition Elements in The Magnetic Field, Journal of Molecular Structure (2019), https://doi.org/10.1016/j.molstruc.2019.127458

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Relative K X-ray Intensity Ratios of The First and Second Transition Elements in The Magnetic Field

Mine UĞURLUa*, Lütfü DEMİRa 1Faculty

of Sciences, Department of Physics, Atatürk University, TR-25240 Erzurum, Turkey

Abstract In this research, EDXRF (Energy Dispersive X-Ray Fluorescence) technique was used for obtaining Kβ-to-Kα X-ray intensity ratios (IKβ/IK) of 3d and 4d transition metal elements prepared at 200 bar pressure and high temperatures at the magnetic fields and without magnetic field, firstly. 3d and 4s4p electron numbers for 3d transition elements were calculated by comparing of (IKβ/IK) obtained with (MCDF) multi-configurations Dirac-Fock calculations values, secondly. The results measured without magnetic field were compared with the theoretical predictions of some studies and were found approximately compatible with the early studies. Finally, it was seen that the magnetic field affects IKβ/IK values and valence electron number of the transition metal elements.

Keywords: EDXRF, intensity ratios, valence-electron configuration, magnetic field.

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1. Introduction The transition metals are mainly known for their hardness, high density, good thermal conductivity, high melting and boiling temperatures. Each of these features ensures that the element and its compounds have special uses. Although some of them have limited usage areas, others have a very important place in our lives. All of the transitional elements carry electrons on the outer d orbital in the electron array. The electrons entering the reactions are also electrons in the d orbital. Transition metals often have more than one oxidation step. 3d transition elements named first transition elements have electronic array ([Ar]4s23dn, [Ar]4s13dn + 1 and [Ar]4s03dn + 2) from Sc to Zn. 4d transition elements called second transition elements have electronic array ([Kr]5s24dn, [Kr]5s14dn + 1 and [Kr]5s04dn + 2) from Y to Cd. The number of valence electrons in the transition metals change from (s2d1) to (s2d10). There are nine orbitals (1 ns, 3 np and 5 (n-1)d) in the transition elements. To form a metal, it is necessary to locate the nine orbital of an infinite number of atoms in space so that the orientation and overlap of each orbital can be specified. The orbital structures are to locate the nuclei on lattice points. At the same time, thanks to the overlap feature, the orbital interactions that fix the lattice are established. Bonding, anti-bonding, and non-bonding bands form. The variation of the electron population in these bands reflects the binding energy and the stability of the lattice. That is, electron density and orbital overlap both become criteria for lattice stability. The d, p, and hybrid orbitals become the orbitals that determine structure [1].

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In the transition elements, narrow d bands overlap with wide s-p bands. The hybridization is responsible for structural and electronic transitions when thermodynamic conditions change. The main reason of this is due to unstable shifts in the relative energy of the occupied d and s-p electron bands [2-4]. The increase in pressure causes the bottom of the d band to increase relative to the d band center. d electron number increases due to sp-d electron transfer [4-5]. One of the mechanisms occuring X-rays is electron transitions between the energy levels of the atom when the atom excites with different ways. If this transition happens from L energy level to K energy level, radiation is emitted and it is called K X-rays or from M or N to K, radiation emitting is called Kβ X-rays. These transitions and names of X-rays are shown in Table 1. The variation of the 3d electron number changes 3p orbitals much stronger than 2p orbitals. So that, main changes are seen at the transition of Kβ and this changes X-ray intensity ratio [9]. Since the early days of X-ray spectroscopy, K/K X-ray intensity ratios (IKβ/IK) have been studied experimentally for elements and then for alloys and various compounds. Because, this quantity can be easily determined with satisfactory accuracy. Accurate measurement of the relative intensities of K X-rays is important for understanding the atomic inner layer ionization processes and for testing existing theories. In addition, accurate determination of IKβ/IK is very important for the practical applications of X-rays such as molecular and radiation physics research, chemical and medical analysis, radioactive ore analysis, metallurgy alloy analysis and elemental analysis. Because IKβ/IK; the chemical structure is closely related to the parameters such as molecular structure and the kind of bonds that the central atom is connected to the surrounding atoms. In short, IKβ/IK are

Journal Pre-proof strongly linked to the atomic structure and are extremely important for the accurate formation of the atomic model. Furthermore, information of this value is beneficial at the understanding of the atomic events like interaction of atom and radiation, pressure, temperature and electric or magnetic field. A lot of studies have been done about IKβ/IK. Some of these studies are without magnetic field [6-14] and with magnetic field [15-17]. There is a strong relationship between IKβ/IK and electronic structure of all 3d elements. The relationship between IKβ/IK and valence electronic structure is stated with parabolic curve [12,18,36-38]. The valence electron structure can be found by using intensity ratios. This assumption is based on by comparing the calculated ratios with the conclusion of MCDF calculations [6,9,18-23]. When the magnetic field is applied to an atom, the degeneration occurs at the energy levels and the new energy levels are formed in the atom. Because of spin and orbital magnetic 



moment of the electron, a torque ( =-  L  B ) which try to align the dipole with the magnetic field. µl is the orbital magnetic dipol moment of an electron and B is the external magnetic field. Associated with this torque, depending on the direction of the magnetic field, some electrons gain energy and some lose energy. The potential energy of orientation is given by following equation; 



E=-  L .B

(1)

The energy suppression is tolerated paired electrons inner layers. However unpaired electrons feel this energy suppression on it. The matters are named like ferromagnetic, antiferromagnetic, paramagnetic etc. according to behaviors in the magnetic field. It is subject of curiosity that how changes happen at an atom in the magnetic field. The properties of the matter can be changed in the magnetic field. It has importance at developing

Journal Pre-proof magneto electronics. For example, if ferromagnetic layers are parallel to the field, matters have the lowest resistance or anti-aligned, the matter has the highest resistance [39]. In this work, it was tried to understand what happened at the atom interacting with radiation when magnetic field is applied to it. So IKβ/IK of 3d and 4d transition elements have been investigated at the magnetic fields (B= 0, 4000, 8000 Gauss). This study is the first in terms of elements used, preparing of the elements and magnetic field values aspects. Furthermore, it is important to inspire future works. 2. Experimental details and data analysis The samples in powder form (particle size10 µm) that are 3d transition elements (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) and 4d transition elements (Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag and Cd) were obtained. SEM photos of some elements used in this study are given in Fig. 1. The samples were turned into pellet form with radius 13 mm by applying pressure with 200 Bar. After samples were annealed 1000°C (excluding Zn and Cd ~350 °C) through 30 minutes in the oven and leaved to cool in the room temperature and atmosphere pressure. Some of the samples photos after annealing process are shown in Fig. 2. Then the samples were mounted on the sample holder (Al) at the midpoint between the poles of the electromagnet capable of producing the magnetic field of approximately 28000 Gauss at 2 mm pole range. During this study, the magnetic field values of, 4000 and 8000 Gauss were applied to the elements. The value of the applied magnetic field was measured with Bell Gauss/Teslameter. In order to minimize the fluctuation in the magnetic field due to the heating of the electromagnet during operation, the ammeter value of the electromagnet itself, which is the control unit of the electromagnet, is always kept the constant. The fluctuation in magnetic field was measured as 55 Gauss. The experimental geometry is given in Fig. 3.

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This system consists of electromagnets, Si(Li) detector which is shielded by a graded filter of Pb, Fe and Al, to obtain a thin beam of photons scattered from the target and to prevent undesirable radiation, sample holder and 200 mCi

241Am

capsule collimator. In this array, 59.54 keV  -rays from

radioactive point source in Pb

241Am

excites to the sample atoms

and sample emits radiation. The angle of sample normal and direction of  -rays is 450 (θ1) and the normal of detector is 450 (θ2). To calibrate the detector, VEX source (Cu, Rb, Mo, Ag, Ba and Tb are excited by means of 241Am

in turn) and test sources (133Ba,

241Am

and

152Eu)

were used. The energy calibration

curve is given in Fig. 4. Furthermore, the accuracy of the detector system (shift and distortion of pulse height distribution, instability and drift in instrumental components, condition, and parameters) was checked with the characteristic spectra of VEX and test sources. The radiation emitting from sample goes to the detector and is placed to the channels according to their energies by means of pre-amplifier and multichannel analyzer. Canberra DSA-1000 PC-based multichannel analyzer records the spectra. The system parameters are adjusted and controlled by the means of Genie-2000 computer program. The data are collected into 4096 channels of the MCA. In this way, the stability of the spectrometer is controlled regularly by noting the number of counts from the elements characteristic peak. In order to obtain the correct peak areas is required to a careful fitting methodology.

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In this study, all the X-ray spectra were carefully analyzed by means of the Microcal Origin 9.0 software peak fitting program (This program is used a multi-Gaussian least-square fit method to obtain the accurate peak intensity). The spectra were obtained for all elements at all magnetic field values. The spectra of Mn element at different magnetic fields are given in Fig. 5. The IKβ/IK were calculated by determining peak areas fitted to Gaussian function after applying necessary corrections (which are all application for determining accurate peak area via PFM (Peak Fitting Module) in Microcal Origin 9.0 software peak fitting program) to the data. Empty counts were taken from the poles of the electromagnet to determine the effect of scattering and the characteristic X-rays released from the poles. The IKβ/IK was obtained by using this formula:

I Kβ I Kα

=

N Kβ β Kα ε Kα N Kα β Kβ ε Kβ

(2)

where N Kβ / N Kα is the counts ratio of the K X-rays, βKα / βKβ is the self-absorption correction factor ratio of the element for the stimulated and emitted photons, and

εKα / εKβ is

the detector yield value ratio for the K X-rays, in turn in order.  is given by:

βKi =

1- exp  -( μ ρ)i /cosθ1+(μ ρ)e /cosθ2 )t  ((μ ρ)i /cosθ1+(μ ρ)e /cosθ2 )t

(3)

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where

(μ ρ)i e are the mass attenuation coefficients (cm2/g) of γ rays and K X-rays

respectively. θ1 and θ2 are mentioned before and t is the mass thickness of the element in g/cm2.

(μ ρ)i e is obtained by helping of WinXCom [24-25]. εKα / εKβ is obtained by using

this formula:

I 0G Ki 

N Ki

(4)

 K  K ti i

i

I0Gε called photon flux that consist of I0 (intensity of stimulating photon), G (Geometry factor) and ε (detector efficiency). In this formula, NKi is the peak area,  K is the fluorescence i

cross section at energy value interested in. All parts of the system were stable during the experiment and the measurements repeated with every sample, with magnetic field value, without sample and without magnetic field for determining experimental errors. In this study, experimental error was calculated by using equation following:

 IK    IK  

 N 2  N 2   2 K K K             N N    K    K   K   2 2     K    I 0G K   I 0G K             K   I 0G K   I 0G K         

12

    2        

(5)

where ∆𝑁𝐾𝛽, ∆𝑁𝐾𝛼 are counts error of 𝐾𝛽 and 𝐾𝛼 X-ray intensity peaks; ∆𝛽𝐾𝛼, ∆𝛽𝐾𝛽 are the βKi errors for 𝐾𝛽 and 𝐾𝛼 X-ray photons; ∆𝐼0𝐺𝜀𝐾𝛼 and ∆𝐼0𝐺𝜀𝐾𝛽 are the effective photon flux errors at 𝐾𝛼 and 𝐾𝛽 energies. The total of the uncertainties (between 0.5% and 0.9%) in different factors such as the evaluation of peak areas (<0.4%), I0Gε product (<0.5%), absorption correction factor (<0.2%) and experimental geometry (<0.1%).

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The calculated IKβ/IK for Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu pure elements have been commented by using MCDF conclusions [19,26-31] which has performed for various valenceelectron structures of the 3dn-r (4s,4p)r (where n is the total number of valence electrons and r=4, 3, 2, 1, 0 according the 3d element valence electron structure). The 3d electron populations of the pure elements have been evaluated by solving the quadratic equation of the form [18]:

kx 2  lx  m  y

(6)

y is the IKβ/IK for 3d transition element, x is the 3d electron number (unknown) and k, l, and m are the coefficients second order polynomial. The theoretical IKβ/IK is fitted with different valence-electron configurations (for example, for Mn the configurations are 3d5 (4s,4p)2, 3d6 (4s,4p)1 and 3d7 by interpolation and the experimental IKβ/IK for y has been written in Eq. (5) to find x.

3. Results and Discussion In this study, the magnetic field effect on IKβ/IK for 3d and 4d transition elements was investigated. IKβ/IK of transition elements at B=0, 4000 and 8000 Gauss are shown in Table 2. The changing of IKβ/IK with atomic number (3d and 4d elements) increasing at magnetic field is given in Fig. 6 and Fig. 7, respectively. When Table 2, Fig. 6 and Fig. 7 is looked at, it is seen that IKβ/IK are different for all elements and as atomic number of elements increase, IKβ/IK of the elements increase at all magnetic field values.

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This relation have seen some earlier works [13-14,16,32-34] and this ratio decreases with the increment of the magnetic field for all elements. Perişanoğlu et al. [15] have investigated the effects of external magnetic field (B= 0.5 T and 1 T) and exciting photon energies on IKβ/IK of various alloy compositions of Ti-Ni transition metal alloys and they found that there is relationship between IKβ/IK of Ti and Ni inTixNi1-x alloys and the external magnetic field. Porikli and Kurucu [16] have worked the effect of an external magnetic field (0.6 T and 1.2 T) on the K shell energy shift (∆E), FWHM (Wi), asymmetry index, and IKβ/IK for diamagnetic (Cu and Zn), paramagnetic (V and Mn), ferromagnetic (Fe, Co and Ni), and antiferromagnetic (Cr) elements. They have found that the external magnetic field effects on X-ray emission spectra and the atomic parameters can change (IKβ/IK decrease with the increasing magnetic field) when the irradiation in a magnetic field. Porikli and Kurucu [17] have searched effects of the external magnetic field and chemical combination on IKβ/IK of some nickel and cobalt compounds. The results have shown that there is relationship between IKβ/IK and magnetic field (0.6 T and 1.2 T). So atomic radiation is affected by the magnetic field and this case causes changes in the intensity ratio, the shapes and the circulation properties of the electronic charge clouds, spectral line-width, radiation rates, atomic lifetimes, photoionization cross sections and fluorescence yields [35]. 3d and 4s4p electron numbers of 3d transition elements, Δn3d (Variation of the number of 3d electrons according to the number of electrons in B= 0 Gauss), Δn(4s,4p) (variation of the number of 4s4p electrons according to the number of electrons in B= 0 Gauss) at different magnetic fields are displayed in Table 3.

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The variation of 3d and 4s4p electron numbers with the atomic number (3d elements) increasing at the magnetic field is given in Fig. 8 and Fig. 9. When Table 3, Figs. 8-9 are looked at, it is seen that 3d electron numbers are different for all elements and 3d electron number of elements increase with the atomic number increasing at all magnetic field values and with the magnetic field increasing for all elements. 4s4p electron number has decreased with the increment of the magnetic field value. Furthermore, If Figs. 6-9 are examined it is seen that it exists nearly in linear correlation between IKβ/ IKα, 3d and (4s,4p) electron numbers and field. This relationship for all elements is such as;  I K  aB  b  a  0   I K   d I K  I K aa0  dB 





These results may be accurate by applying different magnetic field values to the samples. When all graphs and tables are evaluated together, it may be said that external magnetic field causes electrons delocalization. In 3d and 4d transition metals, it is observed overlap between narrow d bands and broad s–p bands [4,5,11]. This overlap might have occured during the preparation of the samples with the application of high pressure and high temperature. In this work, magnetic field used is insufficient (∆E=~10-5eV) to make electron transfer. However, delocalizing of electrons due to the hybridization of sp and d bands for transition elements may be occurred.

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The electrons may be rearranged between 3d and (4s,4p) states of the individual metal atoms with the magnetic field. So that, the intensity of radiation emitting from the samples may change and IKβ/ IKα may change by depending on these results. Furthermore, that IKβ/ IKα decrease and 3d electron number increase with the increment of magnetic field draws attention. 4. Conclusions 3d and 4d transition metals have very high importance at the developing technology and industry due to the wide using areas. So the knowledge of transition elements properties (as depending on atomic parameters) and how to change these properties by depending on external variations (such as pressure, temperature, electric and magnetic field) is a subject needed. In this work, IKβ/ IKα of 3d and 4d transition elements have been investigated at the magnetic fields. The results have showed that IKβ/ IKα depends on the atomic number and the magnetic field and this value can be used for determining valence electron population of 3d elements or may be 4d elements in the future. The valence electron number for 3d transition elements has changed at the opposite direction comparing the intensity ratio with the magnetic field. These variations are interesting and may be related to delocalization phenomena (rearrangement electrons between 3d and 4s,4p /may be 4d and 5s,5p) in the structure of the metals which have been prepared at the high temperatures and high pressure. For the future researches, the repeating of study by applying different magnetic field values will be benefical.

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Figures captions Fig. 1. Some of 3d and 4d transition elements in powder form used in this study. Fig. 2. The samples photo after the annealing process. Fig. 3. The experimental geometry. Fig. 4. The energy calibration curve. Fig. 5. The spectra of Mg element at the different magnetic fields. Fig. 6 The changing of IKβ/IK with atomic number (3d elements) at the magnetic field. Fig. 7. The changing of IKβ/IK with the atomic number (4d elements) at the magnetic field. Fig. 8. The changing of 3d electron numbers with the atomic number (3d elements) at the magnetic field. Fig. 9. The changing of 4s4p electron numbers with the atomic number (3d elements) at the magnetic field. Tables Table 1. Displaying of Siegbahn and IUPAC of X-ray diagram lines. Table 2. IKβ/IK of the transition elements at B= 0, 4000, 8000 Gauss. Table 3. 3d and 4s 4p electron numbers of 3d transition elements at B= 0, 4000, 8000 Gauss

Term

Relative K X-ray Intensity Ratios of The First and Second Transition Elements in The Magnetic Field

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Relative K X-ray Intensity Ratios of The First and Second Transition Elements in The Magnetic Field (Mine UĞURLU and Lütfü DEMİR)

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Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:

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Fig. 1. Some of 3d and 4d transition elements in powder form used in this study.

Fig. 2. The samples photo after the annealing process.

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Fig. 3. The experimental geometry.

Journal Pre-proof Fig. 4. The energy calibration curve.

Fig. 5. The typical K X ray spectra of Mn.

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Fig. 6. The changing of IKβ/IK with the atomic number (3d elements) at the magnetic field.

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Fig.7. The changing of IKβ/IK with the atomic number (4d elements) at the magnetic field.

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Fig. 8. The changing of 3d electron numbers with the atomic number (3d elements) at the magnetic field.

Fig. 9. The changing of 4s4p electron numbers with the atomic number (3d elements) at the magnetic field.

Journal Pre-proof Highlights

*Much data isn’t available about the K X-ray intensity ratios of 3d and 4d transition elements at the external magnetic field in the literature. *The K X-ray intensity ratios of were calculated for 3d and 4d elements at external magnetic field. *3d valence electronic structure were obtained for 3d transition elements by using results of theoreticial (MCDF) multi-configurations Dirac-Fock technique. *The experimental results are approximately agreed with the theoretical predictions in B= 0 Gauss.

Table 1. Displaying of Siegbahn and IUPAC of X-ray diagram lines.

Siegbahn

IUPAC

K1 K2 K1 K2’ K2 K3 K4 K4 K5 K5

K-L3 K-L2 K-M3 K-N3 K-N2 K-M2 K-N5 K-N4 K-M5 K-M4

Table 2. IKβ/IK of the transition elements at B= 0, 4000, 8000 Gauss. 0 Gauss Samp. 21Sc 22Ti 23V 24Cr 25Mn 26Fe 27Co 28Ni 29Cu 30Zn 39Y

40Zr

41Nb 42Mo 44Ru 45Rh 46Pd 47Ag 48Cd

Exp. 0.1282 ± 0.006 0.1291 ± 0.008 0.1303 ± 0.007 0.1321 ± 0.007 0.1332 ± 0.008 0.1348 ± 0.009 0.1356 ± 0.006 0.1379 ± 0.008 0.1394 ± 0.007 0.1415 ± 0.007 0.1853 ± 0.007 0.1866 ± 0.008 0.1890 ± 0.009 0.1917 ± 0.007 0.1988 ± 0.009 0.2019 ± 0.008 0.2066 ± 0.007 0.2099 ± 0.008 0.2127 ± 0.006

IKβ/IK Ref.[32] 0.121 0.128 0.131 0.133 0.133 0.135 0.134 0.136 0.191 0.193 0.198 0.212 0.207 0.217 0.217

4000 Gauss

8000 Gauss IKβ/IK Exp. 0.1232 ± 0.007 0.1256 ± 0.006 0.1271 ± 0.005 0.1289 ± 0.006 0.1300 ± 0.006 0.1312 ± 0.007 0.1324 ± 0.008 0.1346 ± 0.007 0.1362 ± 0.009 0.1374 ± 0.006 0.1822 ± 0.008 0.1831 ± 0.006 0.1840 ± 0.007 0.1877 ± 0.009 0.1939 ± 0.007 0.1966 ± 0.006 0.2026 ± 0.007 0.2039 ± 0.008 0.2093 ± 0.005

Ref.[33] 0.0828 0.0945 0.1053 0.1135 0.1219 0.1283 0.1317 0.1328 0.1339 0.1352

Ref.[34] 0.1355 0.1367 0.1337 0.1385 0.1391 0.1401 0.1379 0.1410

IKβ/IK Exp. 0.1249 ± 0.005 0.1269 ± 0.007 0.1286 ± 0.006 0.1300 ± 0.005 0.1313 ± 0.006 0.1329 ± 0.007 0.1341 ± 0.007 0.1365 ± 0.009 0.1380 ± 0.006 0.1357 ± 0.005

0.1791 0.1838 0.1886 0.1930 0.2018 0.2055 0.2091 0.2110 0.2155

0.1913 0.1981 0.2130 -

0.1842 ± 0.006 0.1849 ± 0.006 0.1866 ± 0.007 0.1891 ± 0.006 0.1957 ± 0.007 0.1987 ± 0.008 0.2046 ± 0.006 0.2061 ± 0.008 0.2105 ± 0.005

Table 3. 3d and 4s4p electron numbers of 3d transition elements at B= 0, 4000, 8000 Gauss.

B=0 G Sc Ti V Cr Mn Fe Co Ni Cu

n3d

1.1382 2.3356 3.4305 4.2788 5.2583 6.0192 7.0088 7.4723 8.1349

n(4s,4p)

1.8618 -0.3356 -0.4305 0.7212 -0.2583 -0.0192 -0.0088 0.5277 0.8652

n3d

1.7767 2.8259 3.8756 4.8412 5.8125 6.5782 7.4569 7.8769 8.5411

B=4000 G n(4s,4p) Δn3d

1.2233 -0.8259 -0.8756 0.1588 -0.8125 -0.5782 -0.4569 0.1231 0.4589

0.6385 0.4903 0.4451 0.5624 0.5590 0.4481 0.4046 0.4062 0.4062

Δn(4s,4p) -0.6385 -0.4903 -0.4451 -0.5624 -0.5542 -0.5590 -0.4481 -0.4046 -0.4062

n3d

2.1680 3.1584 4.3107 5.1941 6.2323 7.2070 8.0621 8.5 9.1386

B=8000 G n(4s,4p) Δn3d

0.8320 -1.1584 -1.3107 -0.1941 -1.2323 -1.2070 -1.0621 -0.5 -0.1386

1.0298 0.8227 0.8802 0.9153 0.9740 1.1878 1.0533 1.0277 1.0037

Δn(4s,4p) -1.0298 -0.8227 -0.8802 -0.9153 -0.9740 -1.1878 -1.0533 -1.0277 -1.0037