ABSTRACT

PHYSICS

GRIFFIN, CHRISTINE D. B.S. SPELMAN COLLEGE, 2010

BREIT-PAULI ATOMIC STRUCTURE CALCULATIONS FOR Si III

Committee Chair: Swaraj S. Tayal, Ph.D.

Thesis dated December 2016

Theoretical study of energy levels, oscillator strengths, transition probabilities,

and lifetimes of Si III lines has been reported in this thesis. These atomic parameters are

required for the interpretation of emission and absorption lines of Si III and for the

modeling of astrophysical plasmas including Galactic High Velocity Clouds (HVCs), the

Sun, and white dwarf stars. We used Hartree-Fock (HF) and Multiconfiguration Hartree-

Fock (MCHF) methods in our calculations. We have considered 58 levels of the 3s2,

3s3p, 3p2, 3s3d, 3s4s, 3s4p, 3s4d, 3s4f, 3s5s, 3s5p, 3s5d, 3s6s, and 3s5f configurations.

The relativistic corrections are included in Breit-Pauli approximation by using one-body

Darwin, mass correction, spin-orbit operators, and two-body spin-other-orbit and spin-

spin operators. The results have been compared with previous theoretical results and

available experimental data, and generally a good agreement is found.

 BREIT-PAULI ATOMIC STRUCTURE CALCULATIONS FOR Si III

A THESIS

SUBMITTED TO THE FACULTY OF CLARK ATLANTA UNIVERSITY

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR

THE DEGREE OF MASTER OF SCIENCE

BY

CHRISTINE DEBRA GRIFFIN

DEPARTMENT OF PHYSICS

ATLANTA, GEORGIA

DECEMBER 2016
 © 2016

CHRISTINE DEBRA GRIFFIN

All Rights Reserved

 ACKNOWLEDGEMENTS

I would like to take this time to thank all who have offered words of

encouragement, advice, and have supported me during the course of my master’s

program.

To my thesis advisor, Dr. Tayal, thank you for the time and effort that you

devoted to supporting me through this process. Dr. Wang and Dr. Msezane, thank you for

being a part of my thesis committee and offering your guidance and support.

Thank you to my fellow classmates and my research partner, Emile Maroha, for

their encouragement and support to me.

Thank you to all my graduate and undergraduate professors, especially Dr.

Mickens, Dr. Mandock, Dr. Williams, Mr. Harrington, and Dr. Ravi for their support.

Thank you, Ms. Heard, for your encouragement and support.

Lastly, I would like to thank my friends, family, and my husband, Darrius, for

their love, understanding, and continuous support.

This work was supported by NASA under grant NNX11AB62G from the Solar

and Heliophysics program and partially supported by NSF DMR 0934142.

ii
 TABLE OF CONTENTS

ACKNOWLEDGEMENTS ................................................................................................ ii

TABLE OF CONTENTS ................................................................................................... iii

LIST OF FIGURES………………………………………………………………………iv

LIST OF TABLES .............................................................................................................. v

LIST OF ABBREVIATIONS ............................................................................................ vi

CHAPTER

I. INTRODUCTION…………..………………………………………………...1

II. BACKGROUND……………………………………………………………...5

A. Si III ........................................................................................................... 5

B. Allowed and Forbidden Transitions .......................................................... 5

III. COMPUTATIONAL METHODS…………………………………………...14

A. Non-relativistic Approach ....................................................................... 14

B. Relativistic Approach .............................................................................. 18

C. Calculation Details .................................................................................. 23

IV. RESULTS AND DISCUSSION……………………………………………..25

A. Wave Functions ....................................................................................... 25

B. Excitation Energies and Lifetimes .......................................................... 27

C. Oscillator Strengths and Transition Probabilities .................................... 32

V. CONCLUSION………………………………………………………………38

REFERENCES ................................................................................................................. 39

iii
 LIST OF FIGURES

Figure

1. COS Data on HVC.....................................................................................................2

2. Smoothed FUSE Spectra............................................................................................3

3. Fine-structure Splitting of 3s3p 3Po State.................................................................22

4. 1s, 2s, and 3s Radial Wave Functions .....................................................................25

5. 2p, 3p, and 4p Radial Wave Functions.....................................................................26

6. 3d, 4d, and 5d Radial Wave Functions.....................................................................26

7. 4f and 5f Radial Wave Functions.............................................................................26

8. Ratio of length and velocity forms of present oscillator strengths...........................36

9. Ratio of present length form to CFF Calculation ……………………....................37

iv
 LIST OF TABLES

Table

I. Comparison of Present Excited Energy Levels of Si III (Ry) ………………..…28

II. Comparison of Lifetimes of Si III Levels…….….…….…..……………..……...30

III. Comparison of Oscillator Strengths & Transition Prob. (s-1)………….....…...…33

v
 LIST OF ABBREVIATIONS

HF Hartree-Fock

MCHF Multiconfiguration Hartree-Fock

Si III Doubly-ionized Silicon

CSFs Configuration State Functions

a.u. Atomic Units

FUSE Far Ultraviolet Explorer

Ry Rydberg

HVCs High Velocity Clouds

COS Cosmic Origin Spectograph

FEFU Femto-erg Flux Units

UV Ultraviolet

IGM Intergalactic Medium

ISM Interstellar Medium

HST Hubble Space Telescope

STIS Space Telescope Imaging Spectrograph

ASF Atomic State Functions

vi
 CHAPTER I

INTRODUCTION

The demand is strong for research that can explain the observed spectral features

produced by atomic lines [1-11]. The Si III lines have been observed in astrophysical

matter such as plasmas, Galactic HVCs, the sun, and white dwarf stars [12-16]. Emission

and absorption lines are observed in the visible and ultraviolet spectra, providing insight

into the nature of the Galaxy. Specifically, the absorption lines provide information about

the nature of the IGM and ISM in the Galaxy. Given the strong presence of observed

lines it is important to calculate atomic parameters for Si III. In this thesis, we will briefly

discuss the motivation; explore previous work done on the Si III system; and through

computational calculations explore the Breit-Pauli atomic properties of Si III.

The evolution of the Galaxy is established by the halo’s contending processes of

accretion and outflow. From observed spectrum lines, information about stellar

metallicities, star formation rates, and mass-metallicity relations can be provided. In the

Milky Way’s halo, emission lines have been observed in Galactic HVCs and provide

information about the atomic properties of the ions present. Knowing the atomic

properties of the ions helps to reveal the conditions of the Milky Way’s halo and its

evolution [13]. In the ultraviolet spectra, Galactic HVCs absorption lines have shown the

presence of Si III.

1
 2
In 2009, during two separate epochs, COS along an AGN target sight line, Mrk

817, passing through Complex C measured absorption lines, seen in Figure 1. In this

figure, from Shull et al. [13] the Si III absorption lines in HVCs Spectra are shown in the

top 2 rows. Prior to the information provided by Figure 1 Shull et al. [14] obtained Si III

lines from the HVCs from HST/STIS. In the HST an UV spectrograph was used to

observe the HVCs. From the work done by Shull et al. [13-14] we can see the significant

importance of Si III in the study of some HVCs.

Fig. 1. From Shull et al. [13] a detail of COS (G130M, G160M) data on HVC at VLSR
= −109 km s−1 (range −190 to −70 km s−1) toward Mrk 817, showing absorption lines
of both low and high ions. HVC Complex C is seen in UV absorption indicated by
pink wash. Fluxes are shown in femto-erg flux units (FEFU) or 10−15 erg cm−2 s−1
Å−1.
 3
In addition to the lines found in HVCs, there have been Si III emission lines

observed in some DB white dwarf stars. With dwarf stars representing the final stages of

approximately 98% of all stars’ lifetime, understanding the ions present is imperative

[17]. In Figure 2, the FUSE [16] observed emission lines are shown in the top panel. The

presence of silicon and other heavy elements in DB white dwarf stars suggest that there

are more physical processes taking place in the white dwarf stars than previously

assumed. Further, knowing about a star’s lifetime is important in the quest to the

understanding of the sun and the universe.

Fig. 2. Smoothed FUSE spectra of five targets from Wesemael et al.[16]. In the
top panel, the carbon and silicon lines identified in the investigation are labeled.
In the second panel, the location of the Lyman lines is marked. In the middle
panel, the location of the strongest geocoronal emission lines is indicated with
the usual symbol. In the fourth panel, the S ii lines observed inGD378 are
marked. In the bottom panel, the observed iron lines are labeled. The G270_124
andGD408 spectra are smoothed with a 15 point and a 12 point average,
respectively, and those of GD 233, GD 61, and GD 378 with an 18 point
average.
 4
The abundant presence of Si III lines in the astrophysical environment demanded

research explaining the spectral features of Si III. There have been various contributors

who have had an impact on the experimental and computational study of Si III atomic

properties. In this thesis, we will only focus on the work of a few contributors. The

experimental studies provided in this thesis are from NIST and W.C. Martin [18-29]. For

a computational comparison, we use the works of C. Froese Fischer, a major contributor

to the field of computational research. We not only compare our results to the results of

Froese Fisher, but, also use the MCHF approach [19] developed by her. The MCHF

approach uses the ideas of HF, MCHF, and quantum mechanics to create computer

programs to study atomic systems. Later on in this research, we will present our

computational work and compare it to the experimental energy levels of NIST and W.C.

Martin and the computational work of C. Froese Fischer.

 CHAPTER II

BACKGROUND

To fully understand the approach and results of the research we will begin with

background information necessary to complete calculations for this research.

A. Si III

Si III is doubly ionized silicon, Si2+. Silicon was discovered in 1811 by two

French chemists Gay Lussac and Louis Jacques Thenard [20]. It makes up approximately

28% of the Earth’s crust and is the 8th most common element in the universe by mass. Its

atomic weight is 28.085 a.u. and it has an atomic number of 14 [21]. For our system, Si

III has a ground state electron configuration of 1s22s22p63s2, giving us a total of twelve

electrons. The core, 1s22s22p6 provides ten electrons while, the outer two electrons come

from 3s2. The two outer electrons allow our system to be modeled as a 2-electron system.

Where the orbital basis is expanded from the ground state up to n=6 in the following

form, 3snl.

B. Allowed and Forbidden Transitions

The angular momentum and parity of a given photon characterizes an

electromagnetic transition between two states. An emitted or absorbed photon is said to

have an electric multipole ( ) transition with the angular momentum and parity,
5
 6
. If the parity of photon is the transition is a magnetic multipole

( ) transition with, the general transition operator, . The electric multipole

transition operator is given below

. (1)

The magnetic multipole form of the transition operator,

(2)

where

(3)

and

. (4)

To understand how the transition occurs between an upper state, and a

lower state, we start with the transition integral [19],

. (5)

The component strength is defined as

. (6)

In the above equation, we assume that the system only consists of energy levels that are

degenerate in the M quantum number. This results in the observable quantity being the

sum of the component strengths over these quantum numbers. The resulting property is

the line strength, given by

 7

. (7)

From the Wigner-Eckart theorem and the orthonality relations, it can be seen that the line

strength is the square of the reduced transition matrix element [19],

. (8)

The transition probability for emission from the upper level to the lower level is given by

(9)

is the statistical weight of the upper level

, (10)

and

. (11)

The oscillator strength can refer to the transition’s absorption or the emission. The

equation below is the absorption oscillator strength,

, (12)

where the atom in the lower state absorbs a photon and is excited to an upper state [19].

The weighted oscillator strength also called the gf-value is given below

(13)

and it is completely symmetrical. The transition has an intensity of the

spectral line that is proportional to the line strength and the gf-value [19]. The lifetime

given below is sum over the multipole transitions to all the lower energy levels [19]
 8
. (14)

The branching ratio, Q for a transition from is given as

. (15)

From this equation the relative intensity of lines from the upper bound can be

derived. From equations (9) and (2) we get

(16)

and

. (17)

For a given multipole transition, the above equations give the relative size for the

rate of transition. Generally speaking, for the electric dipole (E1) radiation is the largest

rate that dominates other rates by a factor of at least . Because of this dominating rate

E1 transitions are labeled allowed and higher order and magnetic transitions are referred

to as forbidden [19].

The Multiconfiguration approximation wave functions are given by the following

expansion [25]

. (18)

the general reduced transition matrix element can be written as [25]

(19)

and is the sum of the reduced matrix elements between the CSFs. The line strength can
 9
enhance and cancel some of the terms because it is the square of the sum of the terms.

These terms can either be positive or negative [19].

We have matrix elements that are LSJ coupled CSFs and to evaluate their matrix

we must recouple J. The transition operators have two types of angular dependencies.

The electric multipole operator, and the magnetic multipole are both

independent of the spin and are reduced in the following way [25]

. (20)

The second term of the magnetic multipole is reduced in the following way

. (21)

And it is in the 9j-symbol k-1, 1 and k are the rank of tensor for spatial, spin, and

total space [19].

Each transition operator is a 1-electron operator

. (22)

Now, the LS reduced matrix elements can be written as sums over the 1-electron matrix

elements. If the CSFs are identical then [19]

. (23)

If the two CSFs differ by orbital pair then

 10
. (24)

Where are angular coefficients and represents the 1-electron

reduced matrix elements, often called transition integrals. The formulae in this section

assume that the basis is a single orthonormal basis [19].

All CSF pairs have selection rules that they have to follow. For a given ASF all CSFs

in the expansion have the same parity. The first rule applies to the parity of the transition

operators. The parity of the two states is given by [19].

The electric dipole operator parity is given below

(25)

And the magnetic operator parity is given by

. (26)

In a given CSF expansion for a particular ASF, the total J-value is common to all

multipole operators. The selection rule follows

, (27)

where and is not allowed.

The following selection rules apply to LS coupling that lead to non-zero values of

. The rules are included because the target orbital are LS generated and we

want to have a complete picture [19].

Within a given CSF the various angular momenta are classified as active or

passive. They are considered passive if they do not “participate” in the transition

resulting in the momenta to be unchanged. Active momenta will obey the rule (27). The
 11
first set of rules applies to the rank of the different operators, with respect of the spatial

and spins space [19]. The operator is spin independent and the spin is considered

passive for the electric multipole. Below is the mathematical summary of the rule

. (28)

For the space angular momenta, the tensor in operator is of rank k and the selection

rule is given below

. (29)

The operator is spin independent and the spin is considered passive the magnetic

multipole. For the space angular momenta, the tensor in operator is of rank k and

the selection rules are summarized as

(30)

The spin operator is of rank 1 in the magnetic multipole transitions CSFs are

linked that differ by spin 1. For the space angular momenta, the tensor in

operator is of rank k-1 and the selection rules are summarized below

(31)

The 1-electron reduced matrix elements for electric multipole radiation are given

as

(32)

where is the reduced matrix element. From here the triangle rule is

introduced for . If and if , where

 12
. There is no rule for Rules for the total angular momenta in the 1-

electron system are the same as equation (29).

For the 1-electron reduced matrix the total angular momenta rules are the same as

(30) and (31). The magnetic dipole, operator is given below [19]

, (33)

and leads to

(34)

From the reduced simple expressions of the elements on the right hand side of (20) and

(21) give the following selection rule

(35)

Below is the total reduced matrix element

(36)

where the magnetic dipole transition only occurs between fine-structure levels of the

same term [19].

The equations below give the strongest transitions for the electric dipole (E1)

(37)

(38)

(39)

where
 13
(40)

The transitions produced by the fine-structure levels form a multiplet. When the J-

dependence of the lines is small, an ensemble is considered as a single body. The

multiplet strength is defined as [19]

. (41)

Similar to the multiplet strength the following equation can be defined

, (42)

where given below is the difference of the weighted energies of the two terms

. (43)

The statistical weight of the lower term is defined as

(44)

From the statistical weight the following formula can be defined

(45)

For the above formula the form is the same as a line and different for the statistical

weight [19].

Now, that we understand more about the transitions involved from one energy

state to another we will move on to the computational methods. Where both the non-

relativistic and relativistic approaches are included to give a full and accurate picture.
 CHAPTER III

COMPUTATIONAL METHODS

To understand the atomic properties of Si III we employ two approaches, a

relativistic and non-relativistic. Our system, Si III is modeled as a 2-electron system.

Normally, if the system is a 1-electron system we could solve it exactly using

Schrödinger’s equation. Since we have more than one electron we must use an

approximation method to solve the system. The idea is that we start with Schrödinger’s

equation and expand it to many electrons [22-27]. This chapter will describe the two

approaches in detail and provide an overview of the methods used.

A. Non-relativistic Approach

From quantum mechanics, it states that a motionless state of an N-electron system

can be defined by the wave function, where and are the

space and spin coordinates of the electron labeled i. This wave function is a solution to

the Schrödinger wave equation,

(46)

The Schrödinger wave equation is an eigenvalue problem where E represents the

eigenvalues of the operator, . The eigenvalues give the possible values for the total

14
 15
energy of the system. The eigenfunction is the wave function, . The

Hamiltonian, which has both discrete and a continuous spectrum is given by

. (47)

Z is the nuclear charge of the atom, is the distance between electrons i and j, and is

the distance of electron i from the nucleus. The Hamiltonian given above is only correct

if it is assumed that the relativistic effects can be ignored. It is also assumed that the

nucleus is a point charge with an infinite mass.

To properly use the approximate wave equation there are properties and

assumptions that must be considered about the wave function. The first is that the wave

functions that are a part of the discrete spectrum are square integrable and correspond to

bound states. It is assumed that these functions are normalized,

, (48)

where the integration and summation is over all space and spin co-ordinates respectively

[23-26]. Once the wave function has been normalized

(49)

we can say that the above equation is the probability of locating the electrons in the

volume element centered at .

Since the electrons cannot be individually distinguished, the Hamiltonian has to be

invariant when the electron co-ordinates in the system are permutated. As a result of the

operator being invariant the following is true

(50)
 16
where is an operator that permutes the wave function. The previous equation shows

that as the wave function is permutated the wave function must also include all linear

combinations of the permutated wave function. Only the linear combinations that are

completely antisymmetric give an accurate picture of the wave function. To represent

such antisymmetric functions

, (51)

where

(52)

is the permutation operator, is the parity of the permutation, and is the number of

electrons. Below is the parity operator,

. (53)

Since the parity operator commutes with both Hamiltonian and angular momentum

operators the eignenfunctions of the parity operator are also a part of the atomic

eignenfunctions. The eigenvalues for this operator are +1 and -1 called even and odd

respectively.

To solve the wave equation using the central-field approximation, we replace the

full Hamiltonian with a separable Hamiltonian. The separable Hamiltonian is given

below

(54)
 17
where is the approximation for the Coulomb effects of the electrons. The new

separable Hamiltonian like the full Hamiltonian commutes with the total angular

momentum operators L2, Lz, S2, and Sz. The new wave approximate wave equation is

given below

(55)

and because the is separable, and are given as the summations of the

individual energies and wave functions shown below [25]

(56)

and

(57)

Each spin-orbital is a solution to the one electron equation,

, (58)

where and the spin orbital is written as follows:

. (59)

The Hamiltonian does not change when the co-ordinates of the electron are permuted.

Thus, the permuted co-ordinates in the product function will also result in an

eigenfunction. Below is the antisymmetric function that was formed by combing the

permuted product functions

. (60)

The antisymmetric function can also be described by the Slater determinant [19, 23]
 18

. (61)

In accordance with the Pauli exclusion principle, the determinant ceases to exist when

This is the case when two electrons have the same space and spin co-ordinates.

For MCHF the wave functions are approximated by a linear combination of orthonormal

configuration state functions [19]

, (62)

where .

B. Relativistic Approach

To address the relativistic effect in our Si III system we will use the Breit-Pauli

Hamiltonian to correct our non-relativistic Hamiltonian. The Breit-Pauli Hamiltonian is

given below [19]

, (63)

where is the non-relativistic many-electron Hamiltonian. is the relativistic shift

operator, it commutes with L and S and is given by

, (64)

is the mass correction term and

(65)

is the one-body Darwin term

 19
. (66)

To describe the interactions between the spin and orbital angular momenta of the system

The fine-structure operator, (seen below) was considered. This operator only

commutes with the total angular momentum operator [19].

(67)

is the nuclear spin-orbit term

(68)

is the spin-other-orbit

(69)

is the spin-spin term

. (70)

The wave functions for the calculations presented in this thesis are Breit-Pauli

wave functions that are linear combinations

, (71)

where

. (72)

Note that are LSJ coupled CFGs. CFGs with different LS terms are

included in the expansion, since neither L nor S are good quantum numbers. Having
 20
different LS terms leads to the mixing of these terms and the wave function provided is

known as the intermediate coupling [19].

(73)

(74)

At this point we should consider the fine-structure levels of our system. This

consideration will help in understanding how the relativistic energy corrections come into

play. If the expansion (71) contains one term the energy expression is as follows [19]

(75)

where is the ordinary non-relativistic energy

(76)

and is the relativistic shift contribution to the relativistic energy correction. It

represents a shift of the non-relativistic energy term since is independent of J

(and Mj). The relativistic shift operators only commute with L and S,

(77)

is the fine structure contribution to the relativistic energy correction

(78)

The fine structure can be expressed as

(79)

where are the energies corresponding to the spin-orbit, spin-other-

orbit and spin-spin operators, respectively [19]. The energy is dependent on the J
 21
quantum number and leads to the splitting of the non-relativistic LS term energy into

the fine structure levels. Below is the rules of addition of angular momenta, it shows the

possible values of J for given values of L and S.

(80)

The number of levels in the term is given by the multiplicity and

and , the spin-orbit and spin-other-orbit, respectively are each products

of rank one and spatial tensor operators

(81)

. (82)

From the Wigner-Eckart theorem [19] and knowing that energy from the spin-spin

operator is a scalar product of two rank two tensor operators is given below.

. (83)

From the explicit expressions for 6-j symbols

(84)

(85)

where , the fine-structure energies can be rewritten

as follows:

(86)
 22
(87)

(88)

and , and are each independent on J.

Neglecting the spin-spin term shows that the energy difference between two

successive fine-structure levels J and J-1 is

, (89)

where is the Landé interval rule for the fine structure and is given by

. The fine structure can be either normal or inverted. It is

normal if is positive and the fine-structure energy increases as the value of J increases.

If is negative the fine structure is said to be inverted [19]. When the spin-spin term

cannot be neglected the Landé interval rule breaks down and the fine structure exhibits

irregular behavior. This behavior is also seen when different CSFs with different L and S,

all couple to the same total J, are included in the expansion [19]. In Figure 3 we have an

example of the fine-structure splitting of one energy level in our Si III system.

Fig. 3. Fine-structure splitting of 3s3p 3Po State

 23
C. Calculation Details

The calculations presented in this research were performed in the relativistic

approach based on the Breit-Pauli Hamiltonian using HF and MCHF codes.

Schrodinger’s equation for the present system is given below

(90)

The Breit-Pauli operators used on the Si III system is given by

(91)

The target spectroscopic orbital basis contains 1s, 2s, 2p, 3s, 4s, 4p, 4d, 4f, 5s, 5p,

5d, 5f, and 6s wave functions. The wave functions were obtained using HF and MCHF

codes and ASF were determined by the lowest energy expansion. The HF code is used for

a single configuration and the MCHF is used for the multiconfigurations. We expanded

from the ground state up to the principle quantum number, n=6. For each principle

quantum number the wave functions were optimized on their lowest energy levels.

The spectroscopic orbitals are generated separately for even and odd parity states.

The correlation orbitals 8s, 8p, 8d, and 8f were generated for even parity states and 7s,

7p, 7d, and 7f correlation orbitals were obtained for the odd parity states. The even parity

had a total of 23 states included in our calculation where 1S had 4 states; 3S had 3 states;
1
D had 4 states; 3D had 9 states; and 3P had 3 states. The odd parity states has a total of 31

states where 3So has 15 states; 1Po has 4 states; 3Fo has 6 states; 1Fo has 2 states; 1Do has 1

state; and 3Do has 3 states. The role of the correlation orbitals is to take account of

correlation energies in various states. The configuration-interaction (CI) expansions were

 24
then generated by promoting one and two electrons from the basic configurations to other

spectroscopic and correlation orbitals.

The diagonalization of the Hamiltonian is given by the following expansion

equation for a symmetric matrix,

. (92)

For a symmetric matrix C there exist an orthogonal matrix O and diagonal matrix D such

that

(93)

and defining the transformed orbital basis,

(94)

along with substitution leads to (92). The antisymmetric expansion is given below

. (95)

In the MCHF atomic structure package the program derives the angular

coefficients from the configuration expansion (71). From the one body Darwin operator

given below

(96)

the angular coefficient is .

 CHAPTER IV

RESULTS AND DISCUSSION

Presented in this section are the results obtained from the present Breit-Pauli

calculations along with other calculations for the Si III system [2, 28]. We provide energy

levels and their lifetimes for the first fifty-eight energy levels. The oscillator strengths

and transition probabilities are provided for transitions between these levels.

A. Wave Functions

The Si III wave functions generated in our calculations are presented in Figures 4-

7. Each figure shows the wave functions as a function of the radius. Each figure

compares three wave functions of the same orbital angular momentum. It can be seen in

the figures that the wave functions follow the rule for the number of nodes given by

Fig. 4. 1s, 2s, and 3s radial wave functions as a function of the radius from the present work
25
 26

Fig. 5. 2p, 3p, and 4p radial wave functions as a function of the radius from the present work.

Fig. 6. 3d, 4d, and 5d radial wave functions as a function of the radius from the present work.
 27

Fig. 7. 4f and 5f radial wave functions as a function of the radius from the present work.

B. Excitation Energies and Lifetimes

The excited energies and lifetimes are presented in Tables I and II and compared

with other works [1-2, 28]. The first fifty-eight (58) energy levels that are presented

were obtained using spectroscopic and correlation orbitals. Results were obtained by

optimizing the even correlation orbitals 8s and 8p on 3s2 1S state and 8d and 8f on 3p2
1
S state. The 7s and 7p correlation orbitals for odd parity states were optimized on 3s3p
3 o
P state and 7d and 7f orbitals were optimized on 3s4p 3Po state. The average of the

calculated energies shows a deviation of 0.00927 Ry from the experimental values.

There is a discrepancy between the present work and experiment in the ordering of fine-

structure levels of the 3s3d 3D and 3s5f 1Fo. The change in ordering of energy levels

could be possibly due to the strong mixing of some of the energy levels.
 28

Table I. Comparison of Present Excited Energy Levels of Si III (Ry) with

Experimental and other Calculations

Index CFS LSJ Excitation Energy Levels (Ry)

Present NIST [28] Diff. [1] [2]

1. 2p63s2 0.00000 0.00000 0.00000 0.00000 0.00000

2. 3s3p 0.47115 0.48046 0.00931 0.46363 0.48028
3 0.47215 0.48163 0.00948 0.46436 0.48147
4 0.47416 0.48402 0.00986 0.46657 0.48388
5 3s3p 0.76247 0.75530 0.00717 0.77590 0.75698
6 3p2 1.09910 1.11370 0.01460 1.09258 1.11618
7 3p2 1.17484 1.18199 0.00715 1.16679 1.18238
8 1.17587 1.18321 0.00734 1.17046 1.18366
9 1.17787 1.18556 0.00769 1.17267 1.18605
10 3s3d 1.30010 1.30264 0.00250 1.30345 1.30899
11 1.30012 1.30262 0.00250 1.30345 1.30893
12 1.30015 1.30260 0.00249 1.30345 1.30895
13 3s4s 1.38655 1.39767 0.01112 1.39677 1.40227
14 3p2 1.40031 1.39829 0.00202 1.42248 1.40203
15 3s4s 1.44018 1.44955 0.00937 1.49302 1.45442
16 3s3d 1.52423 1.51056 0.01367 1.56282 1.51717
17 3s4p 1.58371 1.59681 0.01310 1.59442 1.60114
18 1.58398 1.59711 0.01313 1.59442 1.60149
19 1.58454 1.59778 0.01324 1.59515 1.60220
20 3s4p 1.59663 1.60827 0.01164 1.63336 1.61261
21 3p3d 1.80377 1.81272 0.00895 1.83027 1.81981
22 1.80459 1.81366 0.00907 1.83101 1.82082
 29
23 1.80568 1.81492 0.00924 ……… 1.82213
24 3s4d 1.82585 1.83709 0.01124 1.83248 1.84312
25 1.82586 1.83710 0.01124 1.83248 1.84316
26 1.82589 1.83711 0.01122 1.83248 1.84318
27 3s4d 1.85645 1.86200 0.00555 1.88464 1.86914
28 3p3d 1.85645 1.86836 0.01191 1.85378 1.87507
29 3s4f 1.85814 1.86653 0.00839 ……... 1.87299
30 3s5s 1.86544 1.87881 0.01337 ……… ………
31 3s5s 1.88119 1.89429 0.01310 ……… ………
32 3s4f 1.90147 1.90939 0.00792 ……… 1.91924
33 1.90172 1.90965 0.00793 ……… 1.91957
34 1.90208 1.91001 0.00793 ……… 1.92000
35 3s5p 1.94036 1.95496 0.01460 ……… ………
36 3s5p 1.94608 1.95918 0.01305 ……… ………
37 1.94619 1.95918 0.01299 ……… ………
38 1.94641 1.95913 0.01277 ……… ………
39 3p3d 1.96751 1.97007 0.00256 1.96767 ………
40 1.96849 1.97097 0.00248 1.96914 ………
41 1.96905 1.97153 0.00248 1.96914 ………
42 3p3d 1.97921 1.98096 0.00175 1.97796 ………
43 1.97966 1.98146 0.00180 1.97869 ………
44 1.98012 1.98191 0.00179 1.97869 ………
45 3p4s 2.04861 2.06311 0.01450 ……… ………
46 2.04969 2.06427 0.01458 ……… ………
47 2.05200 2.06694 0.01494 ……… ………
48 3s5d 2.05565 2.06932 0.01367 ……… ………
49 2.05568 2.06934 0.01366 ……… ………
50 2.05573 2.06938 0.01365 ……… ………
51 3s5d 2.06160 2.07464 0.01304 ……… ………
 30
52 3s6s 2.07847 2.09248 0.01401 ……… ………
53 3s5f 2.08161 2.05515 0.02646 ……… ………
54 3p6s 2.08554 2.09924 0.01370 ……… ………
55 3s4s 2.08904 2.09248 0.00344 ……… ………
56 3s5f 2.09451 2.09835 0.00384 ……… ………
57 2.09452 2.09836 0.00384 ……… ………
58 2.09452 2.09838 0.00386 ……… ………
[1] D. C. Griffin, N. R. Badnell, M. S. Pindzola, and J. A. Shaw, J. Phys. B: At. Mol. Opt. Phys. 32,
2139-2152 (1999).
[2] C. Froese Fischer, G. Tachiev, and A. Irimia, Atomic Data and Nuclear Data Tables, 92, 607-612
(2006).
[28] A. Kramida, Yu. Ralchenko, J. Reader, and NIST ASD Team (2013). NIST Atomic Spectra
Database, 5.1, (Online). Available: http://physics.nist.gov/asd. National Institute of Standards and
Technology, (Gaithersburg, MD, September 29, 2013).

The lifetimes of the upper levels are given by

(97)

and are summed over the multipole transitions to all the lower energy levels [19].

Table II. Comparison of Lifetimes (s) of Si III Levels

Index CFS LSJ Lifetimes (s)

Present [20]

1. 2p63s2 ………… …………..

2. 3s3p 1.010E-04 …………..
3 1.020E-04 5.089E-05
4 1.030E-04 7.846E-05
5 3s3p 3.770E-10 4.050E-10
2
6 3p 3.860E-08 3.273E-08
 31
7 3p2 4.480E-10 4.779E-10
8 4.470E-10 4.764E-10
9 4.450E-10 4.741E-10
10 3s3d 3.380E-10 3.494E-10
11 3.390E-10 3.506E-10
12 3.400E-10 3.524E-10
13 3s4s 4.180E-10 4.068E-10
2
14 3p 3.930E-10 4.440E-10
15 3s4s 1.810E-09 1.112E-09
16 3s3d 2.100E-10 2.170E-10
17 3s4p 3.550E-09 3.409E-09
18 3.540E-09 3.390E-09
19 3.520E-09 3.373E-09
20 3s4p 2.130E-09 1.926E-09
21 3p3d 2.320E-07 1.124E-06
22 3.120E-07 2.210E-06
23 4.310E-07 2.378E-06
24 3s4d 2.650E-09 2.783E-09
25 2.660E-09 2.797E-09
26 2.670E-09 2.818E-09
27 3s4d 1.020E-09 1.294E-09
28 3p3d 4.030E-10 4.263E-10
29 3s4f 6.870E-10 5.979E-10
30 3s5s 7.740E-10 ………….
31 3s5s 1.100E-09 ………….
32 3s4f 4.490E-10 9.174E-05
33 4.480E-10 9.483E-05
34 4.470E-10 9.964E-05
35 3s5p 1.280E-09 ………….
 32
36 3s5p 6.810E-09 ………….
37 6.630E-09 ………….
38 6.680E-09 ………….
39 3p3d 2.650E-10 ………….
40 2.630E-10 ………….
41 2.620E-10 ………….
42 3p3d 1.910E-10 ………….
43 1.910E-10 ………….
44 1.910E-10 ………….
45 3p4s 4.870E-10 ………….
46 4.840E-10 ………….
47 4.780E-10 ………….
48 3s5d 8.910E-09 ………….
49 8.940E-09 ………….
50 8.980E-09 ………….
51 3s5d 7.230E-09 ………….
52 3s6s 1.350E-09 ………….
53 3s5f 1.350E-09 ………….
54 3p6s 2.590E-09 ………….
55 3s4s 3.610E-10 ………….
56 3s5f 1.660E-09 ………….
57 1.660E-09 ………….
58 1.660E-09 ………….
[2] C. Froese Fischer, G. Tachiev, and A. Irimia, Atomic Data and Nuclear Data Tables, 92, 607-812
(2006).

C. Oscillator Strengths and Transition Probabilities

 33
We compared our oscillator strengths and transition probabilities with the results

of Froese Fischer in Table III. Generally, there is a good agreement between the two

calculations. The weighted oscillator strength is given below.

. (13)

In Figure 9 the ratio of the present velocity and length form of the oscillator strength

is shown as a function of the present length form. In this figure the data is shown to lie

between the two lines which represent a 20% deviation. The length and velocity forms of

oscillator strengths for weaker transitions show deviations larger than 20%. In Figure 10

the ratio of C. Froese Fischer length form [2] and the present length form of the oscillator

strength is displayed as a function of the present length form. The oscillator strengths

from the two calculations agree to within 20% for stronger transitions. However, the

agreement is worse than 20% for the weaker transitions.

Table III. Comparison of Present Oscillator Strengths and Transition Probabilities (s-1) with CFF
Results

Transition Present [2]

Initial Level Final Level Type gi gk fl Al fl Al

3s2 3s3p E1 1 3 1.68E-05 1.04E+04 2.77E-05 1.72E+04

3s2 3s3p E1 1 3 1.69E+00 2.58E+09 1.61E+00 2.47E+09

3s2 3s4p E1 1 3 3.14E-05 2.15E+05 7.17E-05 4.92E+05

3s2 3s4p E1 1 3 1.45E-02 1.01E+08 2.25E-02 1.57E+08

 34
3s3p 3s3p M1 3 5 8.90E-09 2.38E-05 8.90E-09 2.49E-04

3s3p 3p2 E1 3 5 7.51E-05 1.45E+05 1.31E-04 2.54E+05

3s3p 3p2 E1 5 5 8.04E-05 2.56E+05 1.42E-04 4.57E+05

3s3p 3p2 E1 1 3 5.64E-01 7.46E+09 5.33E-01 7.06E+08

3s3p 3p2 E1 3 1 1.87E-01 2.21E+09 1.77E-01 2.09E+09

3s3p 3p2 E1 3 3 1.41E-01 5.56E+08 1.33E-01 5.27E+08

3s3p 3p2 E1 3 5 2.35E-01 5.62E+08 2.22E-01 5.32E+08

3s3p 3p2 E1 5 3 1.40E-01 9.15E+08 1.32E-01 8.66E+08

3s3p 3p2 E1 5 5 4.21E-01 1.67E+09 3.98E-01 1.58E+09

3s3p 3s3d E1 1 3 8.87E-01 1.61E+09 8.66E-01 1.59E+09

3s3p 3s3d E1 3 3 2.22E-01 1.20E+09 2.17E-01 1.19E+09

3s3p 3s3d E1 3 5 6.65E-01 2.16E+09 6.49E-01 2.14E+09

3s3p 3s3d E1 5 3 8.88E-03 7.97E+07 8.66E-03 7.90E+07

3s3p 3s3d E1 5 5 1.33E-01 7.16E+08 1.30E-01 7.10E+08

3s3p 3s3d E1 5 7 7.44E-01 2.86E+09 7.27E-01 2.84E+09

3s3p 3s4s E1 1 3 1.18E-01 2.66E+08 1.20E-01 2.72E+08

3s3p 3s4s E1 3 3 1.18E-01 7.99E+08 1.20E-01 8.18E+08

3s3p 3s4s E1 5 3 1.19E-01 1.34E+09 1.21E-01 1.37E+09

3s3p 3s4d E1 1 3 6.49E-03 3.20E+07 4.14E-03 2.06E+07

3s3p 3s4d E1 3 3 1.60E-03 2.36E+07 1.01E-03 1.50E+07

3s3p 3s4d E1 3 5 4.82E-03 4.27E+07 3.04E-03 2.72E+07

3s3p 3s4d E1 5 3 6.23E-05 1.53E+06 3.82E-05 9.46E+05

3s3p 3s4d E1 5 5 9.38E-04 1.38E+07 5.76E-04 8.55E+06

3s3p 3s4d E1 5 7 5.29E-03 5.55E+02 3.26E-03 3.45E+07

3s3p 3p2 E1 3 5 4.97E-02 3.08E+07 4.80E-02 2.98E+07

3s3p 3p2 E1 3 1 2.62E-01 2.61E+09 2.25E-01 2.25E+09

 35
3s3p 3s4s E1 3 1 5.10E-02 5.92E+08 7.67E-02 8.99E+08

3s3p 3s3d E1 3 5 1.69E+00 4.64E+09 1.66E+00 4.61E+09

3s3p 3s4d E1 3 5 1.15E-01 6.79E+08 7.49E-02 4.46E+08

3p2 3s4p E1 5 3 8.54E-05 2.67E+05 1.55E-04 4.89E+05

3p2 3s4p E1 5 3 9.24E-02 3.03E+08 8.95E-02 2.95E+08

3p2 3p3d E1 5 5 1.50E-04 5.90E+05 1.78E-04 7.08E+05

3p2 3p3d E1 5 7 2.73E-05 7.66E+04 5.79E-05 1.65E+05

3p2 3s4f E1 5 7 3.83E-01 1.25E+09 4.54E-01 1.49E+09

3p2 3p3d E1 5 5 5.31E-01 2.42E+09 5.04E-01 2.33E+09

3p2 3p3d E1 3 5 1.58E-05 3.01E+04 2.38E-05 4.65E+04

3p2 3p3d E1 5 5 2.72E-06 8.60E+03 3.95E-06 1.27E+04

3p2 3p3d E1 5 7 2.55E-05 5.78E+04 3.82E-05 8.82E+04

3s3d 3s4p E1 3 1 8.65E-02 1.80E+08 8.24E-02 1.70E+08

3s3d 3s4p E1 3 3 6.48E-02 4.51E+07 6.17E-02 4.24E+07

3s3d 3s4p E1 3 5 4.32E-03 1.82E+06 4.12E-03 1.71E+06

3s3d 3s4p E1 5 3 1.17E-01 1.35E+08 1.11E-01 1.27E+08

3s3d 3s4p E1 5 5 3.89E-02 2.72E+07 3.71E-02 2.56E+07

3s3d 3s4p E1 7 5 1.56E-01 1.52E+08 1.48E-01 1.43E+08

3s3d 3p3d E1 3 5 2.46E-03 3.08E+06 1.11E-05 1.40E+04

3s3d 3p3d E1 5 5 3.40E-04 7.10E+05 1.32E-06 2.76E+03

3s3d 3p3d E1 5 7 1.81E-03 2.71E+06 6.39E-05 9.61E+04

3s3d 3p3d E1 7 5 9.02E-06 2.64E+04 3.60E-07 1.06E+03

3s3d 3p3d E1 7 7 2.29E-04 4.80E+05 2.31E-07 4.87E+02

3s3d 3p3d E1 7 9 1.47E-03 2.42E+06 1.93E-04 3.17E+05

3p2 3s4p E1 1 3 6.67E-02 7.88E+06 2.13E-02 2.52E+06

3s4s 3s4p E1 3 1 1.29E-01 1.23E+08 1.30E-01 1.24E+08

 36
3s4s 3s4p E1 3 3 3.88E-01 1.24E+08 3.89E-01 1.24E+08

3s4s 3s4p E1 3 5 6.49E-01 1.25E+08 6.53E-01 1.26E+08

3s4s 3s4p E1 1 3 8.09E-01 5.45E+07 8.36E-01 5.60E+07

3s3d 3s4p E1 5 3 7.97E-02 1.02E+07 6.72E-02 8.20E+06

3s3d 3p3d E1 5 5 3.97E-06 2.91E+03 3.60E-06 2.65E+03

3s3d 3s4f E1 5 7 3.07E-01 2.25E+08 2.48E-01 1.80E+08

3s3d 3p3d E1 5 5 1.86E-02 1.89E+07 1.48E-02 1.52E+07

3s4p 3s4d E1 1 3 1.13E+00 1.74E+08 1.15E+00 1.80E+08

3s4p 3s4d E1 3 3 2.81E-01 1.30E+08 2.86E-01 1.34E+08

3s4p 3s4d E1 3 5 8.43E-01 2.34E+08 8.57E-01 2.41E+08

3s4p 3s4d E1 5 3 1.13E-02 8.62E+06 1.14E-02 8.88E+06

3s4p 3s4d E1 5 5 1.69E-01 7.76E+07 1.72E-01 8.00E+07

3s4p 3s4d E1 5 7 9.45E-01 3.11E+08 9.61E-01 3.20E+08

3s4p 3s4d E1 3 5 2.67E-04 1.12E+05 1.58E-03 4.05E+05

3s4p 3s4d E1 3 5 9.72E-01 3.02E+08 1.03E+00 3.26E+08

[2] C. Froese Fischer, G. Tachiev, and A. Irimia, Atomic Data and Nuclear Data Tables, 92, 607-812
(2006).
 37

Fig. 9. The ratio between length and velocity forms of the present oscillator strengths as a function
of length form of the present oscillator strengths. The solid lines represent a 20% deviation.

Fig. 10. The ratio between length forms of the present and CFF [2] oscillator strengths as a function
of length form of the present oscillator strengths. The solid lines represent a 20% deviation.
 CHAPTER V

CONCLUSION

The observed spectra of astrophysical objects including Galactic HVCs, the Sun,

and white dwarf stars have shown to emit and absorb Si III lines. Several Si III lines are

critical to our understanding of density, temperature, and elemental abundance of

astrophysical plasmas. Atomic properties such as excitation energy levels, oscillator

strengths, transition probabilities, and lifetimes are used in the modeling calculations. All

calculations were a result of the relativistic approach based on the Breit-Pauli

Hamiltonian. Through the HF and MCHF codes we were able to obtain the calculations

presented in this thesis.

The present work has been compared with the data from NIST, the calculated data

of Froese Fischer, along with other computational calculations. The calculations of the

present work, follows the same MCHF relativistic approach for Si III as the data from

Froese Fischer. The present calculated energies have an average deviation of 0.00927 Ry

from the experimental values. When compared to the work of Froese Fischer the

deviation tends to be higher.

38
 REFERENCES

1. D. C. Griffin, N. R. Badnell, M. S. Pindzola, and J. A. Shaw, J. Phys. B: At. Mol.

Opt. Phys. 32, 2139-2152 (1999).

2. Froese Fischer, G. Tachiev, and A. Irimia, Atomic Data and Nuclear Data Tables,
92, 607-812 (2006).

3. P. Ewart, Atomic Physics (University of Oxford, 2008).

4. P. L. Dufton and A. E. Kingston, Mon. Not. R. astr. Soc. 241, 209-214 (1989).

5. W. Weiss, The Journal of Chemical Physics, 47, 3573-3578 (1967).

6. K. L. Baluja, P. G. Burke, and A. E. Kingston, J. Phys. B: Atom. Molec. Phys. 13,

L543-L545 (1980).

7. Callegari and A. G. Trigueiros, The Astrophysical Journal Supplement Series,

119, 181-188 (1998).

8. S. Djeniže, M. S. Dimitrijević, A. Srećković, and S. Bukvić, A&A 396, 331-336

(2002).

9. H. G. Berry, J. Bromander, L. J. Curtis, and R. Buchta, Physica Scripta, 3, 125-

132 (1971).

10. R. O. Jones, Julich, NIC Series, 31, 45-70 (2006).

11. S. S. Tayal, J. Phys. B: At. Mol. Opt. Phys., 40, 2551-2562 (2007).
39
12. J. A. Collins, J. M. Shull, and M. L. Giroux, The Astrophysical Journal, 705, 962-
977 (2009).

13. J. M. Shull, M. Stevans, and et al., The Astrophysical Journal, 739, 105-124
(2011).

14. Trefftz and R. N. Zare, J. Quant. Spectrosc Radiat. Transfer 9, 643-656 (1969).

15. S. Desharnais, F. Wesemael, P. Chayer, J.W. Kruk, and R. A. Saffer, The

Astrophysical Journal 672, 540-552 (2008).

16. Wesemael, N. Petitclerc, P. Chayer, J. W. Kruk, S. Pesant, and B. Tardif,

Astrophysics in the Far Ultraviolet-Five Years of Discovery with FUSE, ASP
Conf. Ser. 348, 239-241, ed. W. H. Moos, G. Sonneborn, and B. G. Anderson
(San Francisco: ASP, 2006).

17. P. L. Dufton, A. Hibbert, A. E. Kingston, and G. A. Doschek, The Atrosphysical

Journal, 274, 420-428 (1983).

18. S. D. Kawaler and M. Dahlstrom, American Scientist, 88, 498-507 (2000).

19. Froese Fischer, T. Brage, and P. Jönsson, Computational Atomic Structure An

MCHF Approach, scanned by Terminator (Institute of Physics Publishing, Bristol
and Philadelphia,1997).

20. N. E. Holden, History of the Origin of the Chemical Elements and Their
Discoverers,41st IUPAC General Assembly in Brisbane (Online-updated 2004)
Available:
http://www.northallegheny.org/cms/lib4/PA01001119/Centricity/Domain/1255/O
rigin_of_Element_Names.doc. National Nuclear Data Center, (Australia, June
29th-July 8, 2001).

21. R. Toon, G. L. Ellis, and J. Brodkin, Foundations of Chemistry (Holt, Rinehart,

and Winston, Inc., New York, 1968).

40
22. W. C. Martin and W. L. Wiese, Atomic Spectroscopy, (Online). Available:
http://www.physics.nist.gov/Pubs/AtSpec/AtSpec.PDF. National Institute of
Standards and Technology, (Gaithersburg, MD, 1999).

23. J. Griffiths, Introduction to Quantum Mechanics, (Prentice Hall, Inc., 1995).

24. Szabo and N. S. Ostlund, Modern Quantum Chemistry, Introduction to Advanced

Electronic Structure Theory, (Dover Publication, Inc., Mineola, New York, 1996).

25. R. A. Serway and J. W. Jewett, Jr., Physics for Scientist and Engineers With
Modern Physics, Seventh Edition, (Thomson and Brooks/Cole, 2008).

26. W. Yang and R. G. Parr, Density-Functional Theory of Atoms and Molecules,

(Oxford University Press, Inc., New York, New York, 1989).

27. J. S. Townsend, A Modern Approach to Quantum Mechanics, (University Science

Books, Sausalito, CA 2000).

28. Kramida, Yu. Ralchenko, J. Reader, and NIST ASD Team (2013). NIST Atomic
Spectra Database, 5.1, (Online). Available: http://physics.nist.gov/asd. National
Institute of Standards and Technology, (Gaithersburg, MD, September 29, 2013).

29. W. C. Martin and R. Zalubas, J. Phys. Chem. Ref. Data, 12, 323-380 (1983).

41