Optimized GTO Basis set

Imagine the ability to predict with high accuracy the spectra and structural properties of a range of heavy
elements like the unstable francium or the yet to be discovered ununennium. The phenomenal computing
power of the present age has made such an unprecedented feat attainable. The computational herculean
tasks of spin-orbit coupling and other relativistic effects and electron-electron interactions can be addressed in
manner that allows for systematic improvement.
One of the most efficacious ab initio methods for relativistic quantum mechanical calculations is that of Spin
Orbit Configuration Interaction (SOCI). SOCI is a method which, unlike the standard Hartree-Fock plus CI
method, incorporates the effects of relativity and intermediate angular momentum coupling together with the
effects of electron correlation. A relativistic effective potential (RECP) is also used in PSOCI to account for the
effects of the core electrons of the atoms and their interactions with valence electrons, which become
pronounced for heavy elements. It is no surprise, considering SOCIs scaling problems with increased numbers
of valence electrons, that it has be adapted for implementation on massive parallel processors, producing a
new procedure dubbed Parallel Spin Orbit Configuration (PSOCI).
In this project, PSOCI is used to calculate the energies of electronic states of the cesium and francium
elements. Its accuracy is demonstrated by comparison to experimental results and another ab initio method
called Self Consistent field in JJ Coupling (SCF-JJ) which also incorporates an RECP to account for relativistic
effects. Calculations were carried out on the supercomputers Hopper (NERSC) and Lonestar (TACC).

Molecular Geometry

ARGOS

Symmetry Definitions

PSOCI on Hopper
and Lonestar is
amazing!!!

J&K
Integrals

& Operator
Nuclear number

CONVERTER

Lets show you how

to run PSOCI

P & Q Integrals
P & Q Integrals

Definition of Occupied Molecular Orbitals

SCF Energy
& Coefficients

SCFPQ-SCF

Electronic State Symmetry Coupling Coefficients

Integral Transformation
over Molecular Orbits

TRANSFORM

TERMS
ARGOS Argonne Ohio State integrals program
SCF

Self Consistent Field program

PQ

P & Q Integrals generator program

Configuration
List

Double group symmetry of state

Reference Configurations
Levels of excitation

CGDBG

Basis Set Size

CGDBG Configuration generator program for the

nuclear double group
PSOCI Parallel Spin Orbit Configuration Interaction
program

Increase the PSOCI configuration from valence configuration interaction to multi

reference singles and doubles to improve accuracy.
Use PSOCI to calculate the spectra energies for francium and cesium dimers. There are
no experimental data for francium dimers due to their instability.
A RECP will be calculated for the yet to be discovered ununennium (element 119).
Together with the calculated RECP, PSOCI shall be used to compute the energy levels
of ununennium and its homonuclear dimer.

[1] Jeffery L Tilson and Walter C Ermler (2014): Massively Parallel SpinOrbit Configuration Interaction.
Theoretical Chemistry Accounts (2014) 133:1-9. DOI 10.1007/s00214-014-1564-8
[2] Kramida A, Ralchenko Yu, Reader J, and NIST ASD Team (2013): NIST Atomic Spectra Database (ver.
5.1), [Online]. Available: http://physics.nist.gov/asd [2014, August 12]. National Institute of Standards
and Technology, Gaithersburg, MD
[3] L. Visscher and K.G. Dyall (1997): Dirac-Fock atomic electronic structure calculations using different
nuclear charge distributions. Atom. Data Nucl. (1997) Data Table, 67, 207

PSOCI

The results of our calculations are shown in Table 1,2, and 3. Config. Stands for Configuration and Experim. Stands for Experiment
Results from experiment, PSOCI and another ab initio method called Self Consistent Field in JJ Coupling (SCF-JJ) are compared in Tables 1 and 2.
PSOCI is overall closer to the experimental values than SCF-JJ. Also PSOCI also predicts the correct energy ordering of the 5d configuration, placing 55 above 53 as
2
2
indicated by experiments.
However, SCF-JJ predicts the reverse ordering. This is due to the fact that although SCF-JJ like PSOCI incorporates a RECP, it does not account for electron
interaction effects which play a significant role in the 5d orbitals.
Table 3 illustrates the pronounced effects of spin orbit splitting as the elements mass increases. Dirac Fock results are also cited for comparison. All energies are in
units of electron volts.
Total ground state energies for Cs are -541.0 eV (SCF-JJ) and -540.8 eV (PSOCI). For Fr the total ground state energies are -517.3 eV (SCF-JJ) and -516.1 eV (PSOCI).

Config. Term J

6p6
6p6

The Texas Advanced Computing Center (TACC) at the University of Texas at Austin and the National
Energy Research Scientific Computing Center (NERSC) at the Lawrence Berkeley National Laboratory is
acknowledged for providing high performance computing resources for this research project.

See section below

for results

6p6

7s 2S
7p 2P
6d 2D

Experim.
SCF-JJ
PSOCI
Energy
Energy % Diff. Energy % Diff.
(eV)
(eV)
(eV)

1/2 0.00

0.00

N/A

0.00

N/A

1/2 1.517

1.261

18.43 1.289

16.25

3/2 1.726

1.413

19.94 1.406

19.99

3/2 2.012

1.873

7.156 1.869

7.369

5/2 2.037

1.859

9.138 1.888

7.592

Config. Ter
m

5p6

6s 2S
5p6 6p 2P
5p6 5d 2D

Experim.
SCF-JJ
PSOCI
Energy
Energy % Diff. Energy % Diff.
(eV)
(eV)
(eV)

1/2 0.00
1/2 1.386

0.00
1.147

N/A
0.00
18.85 1.162

N/A
17.58

3/2 1.454

1.197

19.41 1.203

18.94

3/2 1.798

1.712

4.869 1.735

3.549

5/2 1.810

1.707

5.859 1.742

3.817

Element

Config. Experim. SCF-JJ PSOCI

Energy Energy Energy

Dirac Fock
Energy

5p

N/A

0.0672 N/A

-0.0673

6p

0.068

0.050

0.041

N/A

5d

0.012

-0.005 0.007

N/A

6p

N/A

0.194

N/A

-0.193

7p

0.209

0.152

0.123

N/A

6d

0.025

-0.014 0.019

N/A

CESIUM

FRANCIUM