Monday, October 12, 2026

Single electron ions

Single electron ions are any nucleus surrounded by only one electron, examples are He+, Li2+, Be3+, B4+, …. Energy levels of these ions are calculated like in Hydrogen atom : \(e_n=-\frac{13.6 Z^2}{n^2}\) , where  is the charge of the nucleus. For example He+, \(Z=2\), then \(E_1=-54.4 e V\). And this is the second/last ionisation energy of Helium atom (in ultraviolet range).

0.2323

 

\(\frac{e^{-2 \pi  r}}{r}=\epsilon +1\)
\(r\approx 0.2323\)

137

 \(5! \sum _{n=1}^5 \frac{1}{2 n}=137\)

Hubble constant

Just a quick thought, in ideal and simplified condition, the expansion rate of universe is constant, hence Hubble constant is also constant over time. Therefore Hubble constant can't be used for estimating the age of the universe, because either we measure today or we measure 5 billion years from now, the Hubble constant still shows 1/(13.8 billion years).

Ionisation energies of Lithium atoms in ground state

 I calculated the ionisation energies of Lithium atoms in ground state. Ionisation energy of an atom is the energy required to remove electron(s) from that neutral atom. Lithium has three electrons, hence it has three ionisation energies :

transition

ionisation energy (eV)

electron configuration

spectroscopy term symbol [1,2]

Li ® Li+

5.39 [3,4]

1s22s ® 1s2

2S1/2 ® 1S0

Li+ ® Li2+

75.64 [5]

1s2 ® 1s

1S0 ® 2S1/2

Li2+ ® Li3+

122.45 [6]

1s ® none

2S1/2 ® none

A reminder, spectroscopy term symbol is 2S+1LJ  with S, L, J are total spin, total angular momentum, total spin plus angular momentum. I wanted to obtain these three numbers 5.39, 75.64, 122.45 via computational simulation. The software package that I selected is Nwchem [7]. It runs within Linux Ubuntu. So some minimum understanding of Linux operating system is desirable here. And I ran it within Windows 11 operating system.

In quantum chemistry calculations, I used density functional theory (DFT) [8] with 6-31G basis set [9] and b3lyp hybrid exchange correlation functional [10]. Although other better methods can be used.

Below are my steps of the calculations :


1

installed WSL (Windows Subsystem for Linux – by Microsoft) in Windows 11

in Windows 11 command prompt, type

wsl -- install

2

installed Linux Ubuntu in WSL

 

3

updated/upgraded the linux operating system

sudo apt update

sudo apt upgrade

4

installed parallel processing software to take advantage of my multicore computer, e.g. Open MPI or MPICH (optional)

sudo apt install openmpi-bin libopenmpi-dev

or

sudo apt install mpich libmpich-dev

5

installed Nwchem

sudo apt install nwchem

6

created working directories

C:\Users\username\Documents\nwchem

C:\Users\username\Documents\nwchem\perm

C:\Users\username\Documents\nwchem\scratch

7

went into nwchem directory

cd /mnt/c/Users/username/Documents/nwchem

8

calculated the ground state energy of Li (using 8 processors)

electric charge = 0

electron configuration is 1s22s, then S=1/2, multiplicity = 2S+1 = 2

input file : Li3el.nw [11]

mpirun –np 8 nwchem Li3el.nw > Li3el.out

output file : Li3el.out

Total DFT energy = -7.490902307210 Hartree

ELi = -7.491 ´ 27.211 = -203.838 eV

 9

calculated the ground state energy of Li+ (using 8 processors)

electric charge = 1

electron configuration is 1s2, then S=0, multiplicity = 2S+1 = 1

input file : Li2el.nw [12]

mpirun –np 8 nwchem Li2el.nw > Li2el.out

output file : Li2el.out

Total DFT energy = -7.284534796564 Hartree

ELi+ = -7.284 ´ 27.211 = -198.205 eV

10

calculated the ground state energy of Li2+ (using 8 processors)

electric charge = 2

electron configuration is 1s, then S=1/2, multiplicity = 2S+1 = 2

input file : Li1el.nw [13]

mpirun –np 8 nwchem Li1el.nw > Li1el.out

output file : Li1el.out

Total DFT energy = -4.446963826727 Hartree

ELi2+ = -4.447 ´ 27.211 = -121.007 eV

11

calculated first ionisation energy

E1st = ELi+ - ELi =  -198.205 + 203.838 = 5.633 eV

12

calculated second ionisation energy

E2nd = ELi2+ - ELi+ = -121.007 + 198.205 = 77.198 eV

13

calculated third ionisation energy

E3rd = 0 - ELi2+ = 121.007 eV


 

[1] CN Banwell,  Fundamentals of Molecular Spectroscopy, 3rd ed., McGraw-Hill, 1983, p. 179.

[2] DJ Griffiths, Introduction to Quantum Mechanics, Prentice Hall, 1995, p. 191.

[3] Wolfram Mathematica

ll = SpectralLineData[EntityClass["AtomicLevel", {"Lithium", 1}]];

aa = Length[ll] (* 182 *)

Table[{ll[[i]]["ElectronConfigurationString"], ll[[i]]["TermSymbol"],ll[[i]]["Energy"]}, {i, 1, 182}] // TableForm

browsed through the list, I picked last data.

[4] BH Bransden & CJ Joachain, Physics of atoms and molecules, Longman Scientific & Technical, 1983, p. 302.

[5] Wolfram Mathematica

ll = SpectralLineData[EntityClass["AtomicLevel", {"Lithium", 2}]];

aa = Length[ll] (* 109 *)

Table[{ll[[i]]["ElectronConfigurationString"], ll[[i]]["TermSymbol"],ll[[i]]["Energy"]}, {i, 1, 109}] // TableForm

browsed through the list, I picked last data

[6] Wolfram Mathematica

ll = SpectralLineData[EntityClass["AtomicLevel", {"Lithium", 3}]];

aa = Length[ll] (* 149 *)

Table[{ll[[i]]["ElectronConfigurationString"], ll[[i]]["TermSymbol"],ll[[i]]["Energy"]}, {i, 1, 149}] // TableForm

browsed through the list, I picked last data

[7] https://nwchemgit.github.io/index.html. Among a range of selection of software packages, e.g. Gaussian (https://gaussian.com/), Abinit (https://www.abinit.org/), VASP (Vienna Ab-initio Simulation Package) (https://vasp.at/), ADF (Amsterdam Density Functional) (https://www.scm.com/amsterdam-modeling-suite/adf/), ORCA (https://www.faccts.de/orca/), Quantum Espresso (https://www.quantum-espresso.org/), etc.

[8] https://www.imperial.ac.uk/media/imperial-college/research-centres-and-groups/computational-materials-science/teaching/DFT_NATO.pdf

[9] https://www.basissetexchange.org/

[10] https://mazziotti.uchicago.edu/qcdictionary/b_terms/b3lyp/

[11] Li3el.nw

title "Li with 3 electrons"

permanent_dir ./perm

scratch_dir ./scratch

charge 0

geometry

  Li 0 0 0

end

basis

  * library 6-31G

end

dft

  xc b3lyp

  mult 2

end

task dft

[12] Li2el.nw

title "Li with 2 electrons"

permanent_dir ./perm

scratch_dir ./scratch

charge 1

geometry

  Li 0 0 0

end

basis

  * library 6-31G

end

dft

  xc b3lyp

  mult 1

end

task dft

[13] Li1el.nw

title "Li with 1 electrons"

permanent_dir ./perm

scratch_dir ./scratch

charge 2

geometry

  Li 0 0 0

end

basis

  * library 6-31G

end

dft

  xc b3lyp

  mult 2

end

task dft