Theoretical oscillator strengths for the spin-allowed electric-dipole transitions in the Zn-like ions

Hsin-Chang Chi Department of Physics National Dong Hwa University

Contents
(I) Introduction (II) Relativistic Many-Body Perturbation Theory (III) Procedures of Calculations (IV) Results for Zn-like ions (V) Conclusions (VI) Future Works
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(I) Introduction
(i)

Most Important Effects in The Atomic Structure Calculations

(1) Relativistic effects (2) Correlation effects (a) valence-valence correlation (b) core-valence correlation (c) core-core correlation
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(ii)

Theoretical Approaches
Variational calculations Configuration interaction calculations Multiconfiguration Dirac-Fock calculations Multiconfiguration relativistic random-phase approximation Relativistic many-body perturbation theory calculations

(iii)

Present Calculations
(a) Zinc I isoelectronic sequence has been intensively studied both in theories and experiments. (b) The electric-dipole transitions in the Zn-like ions, GeIII, AsIV, KrVII, RbVIII, and MoXIII are calculated.

(I) Relativistic Many-Body Perturbation Theory

The Schrdinger equation: Partition of the Hamiltonian: Model Hamiltonian:

H =E

H = H0 +VI
H 0 = h(i)
i

Z h = c p + ( 1) mc + U ( r ) r
2

1 VI = + (i, j ) + (i, j ) + (i )U ( ri ) + (i ) rij i< j i

U (r ) : Hartree-Fock Potential

+ :

Positive-Energy Projection Operator

Perturbation expansion in powers of VI

E=E
(0)

+ E +
(1)

=
(1) Zeroth order

(0)

(1 )

(H 0 E )
(0)

(0)

=0

(2) First order

( H 0 E (0) ) (1) = ( E (1) VI ) (0)

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Atomic wave function of divalent atom:

0 ( 0 ) = Cvw (vw) vw

where

(0) vw

= vw jv mv jw mw JM a a 0
mv mw + v + w

1, v w vw = 1 2, v = w
0 : core wave functions
= C1 4 s 2 1
2 3

v, w : valence orbitals
2 + C3 4 p3

Zn-like ions in the zeroth-order ground state :

(0) 2

+ C2 4 p2 1

+C4 4d

2 + C5 4d 5

+ C 6 4 f 52

+ C 7 4 f 72

First-order wave function

(1) = D1vw + D2vw + D3vw + T1vw + T2vw + T3vw + Qvw vw m v m

1vw

: aa 0
m v

1v excitation
w

2 vw

: aa 0
m w

1v excitation

3vw

: aa 0
m n

2v excitation

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1vw

: a aa a 0
m b v w

v b m v

1c excitation

2 vw

: a a aa 0
m n b v

n b

1v-1c excitation

3vw

: a a aa 0
m n c w

m c

n w

1v-1c excitation

Q :a a aaa a 0
vw m n c b v w

m v c
1 vw

If U = VHF , then D

n w 2c excitation b

= D

2 vw

=T

1 vw

=0
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(II) Procedures of Calculations

(1) Configuration interaction calculations The reference states are described by multiconfiguration wave functions that account for the valence-valence correlations. (2) Perturbation calculations The core-valence and core-core correlations are treated by pertubation.

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Perturbation Expansions in Powers of VI Atomic energy: Photon Energy:

EI = EI( 0 ) + E I(1) +
( ( EF = E F0 ) + E F1) +

= + + ( ( 0 ) = E F0 ) E I( 0 ) ( (1) = E F1) EI(1) Transition operator: T ( ) = c A( ) T ( ) = T ( 0 ) ( ) + T (1) ( ) + T ( 0 ) ( ) = T ( ( 0 ) ) (0) ) (1 ) (1) dT ( T ( ) = d

(0) (1 )

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Transition Amplitudes
(1) First order:

F T ( ) I

(1)

= F( 0 ) T ( 0 ) ( ) I( 0 ) =
(0) F

T ( )
(0)

(0) I

(2) Second order:

F T ( ) I

(2)

(1) F

T ( )
(0)

(0) I

(0) F

T ( )
(0)

(1) I

+ (1) (0) F

dT ( (0) ) (0) I d
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First-order Diagram
v w
v w

+
v w

(v w)

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Second-order Valence-Valence Diagrams

v w v w

i
v
v

+
w
w v

i
v w
w

+
i
v

+
w
(v w)
v

i
w
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Second-order RPA Diagrams

v w v w

n n

w v w

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The Core-Shielding Effect

Atoms in an external EM field
+ Eext + + -Eint + + -

Eext

Eext

Within the atom

Etot = Eext + Eint

The RPA terms account for the core-shielding effect.

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(III) Results of Ge+2, As+3, Kr+6, Nb+11, and Mo+12 (a) The fourteen lowest levels considered
1.) (4 s 2 ) 1S0
2.) (4 s 4 p ) 3 P0o

8.) (4 s 4d ) 3 D2
9.) (4 s 4d ) 3 D3

3.) (4 s 4 p ) 3 P o 1 4.) (4 s 4 p ) 3 P2o 5.) (4 s 4 p ) 1P o 1 6.) (4 p 2 ) 1D2 7.) (4 s 4d ) 3 D1

10.) (4 p 2 ) 3 D0

11.) (4 p 2 ) 3 P 1 12.) (4 p 2 ) 3 P2 13.) (4 s 4d ) 1D2 14.) (4 p 2 ) 1S0

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(b) Spin-Allowed E1 transitions: High Low

1.) (4 p 2 ) 3 P0 (4 s 4 p ) 3 P o 1
2.) (4 p 2 ) 1S0 (4 s 4 p ) 1P o 1

9.) (4 p 2 ) 3 P2 (4 s 4 p ) 3 P o 1
10.) (4 s 4d ) 3 D2 (4 s 4 p ) 3 P o 1

3.) (4 p 2 ) 3 P (4 s 4 p ) 3 P0o 1
4.) (4 s 4d ) 3 D1 (4 s 4 p ) 3 P0o

11.) (4 s 4d ) 1D2 (4 s 4 p ) 1P o 1
12.) (4 p 2 ) 1D2 (4 s 4 p ) 1P o 1

5.) (4 p 2 ) 3 P (4 s 4 p ) 3 P o 1 1
6.) (4 s 4d ) D1 (4 s 4 p ) P
3 3 o 1

13.) (4 p 2 ) 3 P2 (4 s 4 p ) 3 P2o
14.) (4 s 4d ) 3 D2 (4 s 4 p ) 3 P2o

7.) (4 p ) P (4 s 4 p ) P 1
2 3 3

o 2

15.) (4 s 4d ) 3 D3 (4 s 4 p ) 3 P2o
16.) (4 s 4 p ) 1P o (4 s 2 ) 1S0 1
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8.) (4 s 4d ) 3 D1 (4 s 4 p ) 3 P2o

(c) The Einstein A-Coefficients

(109 s1)

(4 s 4 p ) 1P o (4 s 2 ) 1S0 for 1

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Oscillator Strengths

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(d) Gauge Dependence of Transition Amplitudes The first-order transition amplitude is obtained using the zeroth-order wave function. The second-order transition amplitude contains four parts: (1) the second-order valence-valence correlation corrections (2) the second-order RPA corrections (3) the derivative terms (4) the Dirac-Fock terms The Dirac-Fock terms vanish in the present calculation since we choose the model potential to be the frozen-core DiracFock potential.
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 The first-order transition amplitude is gauge independent, provided we start from a local potential. 1.) The gauge dependence of the first-order transition amplitudes from the present calculations is due to the fact that we start from a non-local frozen-core Dirac-Fock potential. 2.) The gauge dependence of the resonance transition is greater than those of other transitions.
This may be due to very strong interaction between the (4s2) and (4p2) configurations.
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 The second-order transition amplitude is gauge independent, provided one starts from a local potential and artificially includes the contributions from the negativeenergy states. 1.) The gauge dependence in the present calculations is a result of the nonlocality of the model potential and the restriction to positive-energy states in the no-pair Hamiltonian. 2.) The present calculations show that the inclusion of the second-order transition amplitudes brings the length results and the velocity results into excellent agreement.
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Resonance Transition Amplitudes of As+3

(I) Relativistic MBPT
Term \ Guage 1st-order 2nd-order val-val 2nd-order RPA
(1) term

length 2.450810-3 1.139910-4

velocity 3.010110-3 6.177110-5

1.811710-4

1.498310-4 0.0000

4.251510-4 2.808810-3

total

2.798510-3

Different gauges are in excellent agreement! (II) Experimental value:

(2.70.2)10-3
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Excellent agreement with experiment!

The Theoretical Justification

F T I

(1) + (2)

= F T I
First Order

(1)

+ F T I

(2)

Total Gauge Dependence

Second Order

The zeroth-order term of F||T||I(2) compensates exactly for F||T||I (1). The gauge dependence of F||T||I (1)+(2) is first order in VI. The inclusion of the second-order correction substantially reduces the gauge dependence of the transition amplitude.
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(IV) Conclusions
(1) The length and the velocity results for the transition amplitudes of the Zn-like ions are in excellent agreement in the second-order relativistic MBPT calculations. The RMBPT calculations are gauge independent order by order for calculations starting from a local potential and including the contributions from the negative-energy states.
Positive Energy States Gauge Independence = Local Potential+ Negative Energy States
The remaining gauge dependence is due to the non-local

potential and the exclusion of the negative-energy states.

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(2) The second-order relativistic MBPT transition amplitudes for allowed E1 transitions are in excellent agreement with experiment for all ions under present investigation. The present calculations agree well with experiment for all ions except for the neutral Zn atom. The discrepancy may be due the excluded core-polarization effects. Further investigations are certainly required to understand fully, and remove, the remaining discrepancies.

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(V) Future Works

We will perform second-order relativistic MBPT calculations to study the transition rates for allowed E1 spin-forbidden E1 M1 E2 transitions in atoms with two valence electrons. We will derive the third-order relativistic MBPT formulas to remove the discrepancies between theory and experiment for neutral atoms.

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 We are carrying out second-order relativistic MBPT calculations to investigate neutral Zn and Ga+1. The calculations will provide further realization of the importance of core-polarization effects and corrections beyond second-order.
Radiative Lifetimes (in ns) of Resonance Transition for Ga+1
Length 0.442 Velocity 0.460 Exp. Energy 0.476 0.48 0.12 Experiment 0.49 0.04 0.65 0.08

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 We are applying the second-order relativistic MBPT theory to study the Spin-Forbidden E1 transitions

1.) (4 s 4 p ) 1S0 (4 s 4 p ) 3 P o 1
2.) (4 s 4d ) D2 (4 s 4 p ) P
1 3 o 2

7.) (4 s 4d ) 3 D2 (4 s 4 p ) 1P o 1
8.) (4 s 4d ) 3 D1 (4 s 4 p ) 1P o 1

3.) (4 s 4d ) D2 (4 s 4 p ) P
1 3

o 1

9.) (4 p 2 ) 1D2 (4 s 4 p ) 3 P o 1
10.) (4 p 2 ) 1D2 (4 s 4 p ) 3 P o 1

4.) (4 p 2 ) 3 P2 (4 s 4 p ) 1P o 1

5.) (4 p ) P (4 s 4 p ) P 1
2 3 1

o 1

11.) (4 s 4 p ) P (4 s ) S0
3 o 1 2 1

6.) (4 p 2 ) 3 P0 (4 s 4 p ) 1P o 1
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 We will apply the second-order relativistic MBPT theory to study the photoionization processes in atoms with two valence electrons.
Reference
[1] H. S. Chou, Phys. Rev. A 62 ,042507-1 (2000). [2] H. S. Chou, Phys. Scr. 64, 140 (2001). [3] P. Bogdanovich and H. S. Chou, Lithuanian J. Phys. 47 387 (2007). [4] H. C. Chi and H. S. Chou , Phys. Rev. A 82, 032518 (2010) 82,

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