record

5 minute read

Published: May 12, 2025

Content

2025-05-22
single Cu
single Cl
H2O
2025-05-23
2025-05-25
2025-05-26
2025-05-27
Results
- singleatom
- Cu2+
  - 5L
  - 6L
- Cu1+
- Cl-1
Reference
2025-06-03

DFT calculation of 6 configuration of Cu-Cl-water molacule

system energy
- transition pathway
further
- optical absorption? can be use for UV spectrum reasoning

2025-05-22

free energy (formation energy?) calculation

single Cu

/cucl/May23/cu singlecu2=-401.96197944 singlecu1=-403.07135668

single Cl

/cucl/May23/cl singlecl=-34.88951178

H2O

/cucl/May12/h2o singleh2o=-44.04153750

2025-05-23

drawing atomic model

color
- Cu2+
  - #650065
  - #BE63BE
  - #E3BDDC
- Cu1+
  - #A35331
  - #FFA57F
  - #FF8653
- O
  - #7E7E7E
- H
  - #BFBFBF
- Cl
  - #1EFFEF #23b8ae

2025-05-25

maybe not correct (not pure Cu-Cl complex but with other atoms)
Cu(I)Cl2 bond distance (Cu-Cl) = 2.104 A
- angle=175.9deg
Cu(I)Cl3 bond distance (Cu-Cl) = 2.165+-(12) A
- angle=120(+-1.5) reference: https://www.mdpi.com/2304-6740/13/2/36
Cu(H2O)6
- 6 coordinations structure
  - bond distance
    - in xy plane = 1.97A
    - z = 2.38A
  - /May25
    - relaxing
  - reference https://doi.org/10.1016/S0009-2614(00)01110-6
- 5 coordinations structure
  - /May22/6W5L
    - relaxed scf finished
    - cuh2o6l5=-667.01612658
      - cuh2o6l5-singlecu2-singleh2o*6
        -0.8049221400000306
  - reference https://pubs.acs.org/doi/abs/10.1021/jp1000804
- 4 coordinations structures
  - 2 variants
    - 6W4L1
      - /May22/6W4L1/
      - relaxed scf finished
      - cuh2o6l41=-666.99439952
        cuh2o6l41-singlecu2-singleh2o*6
        -0.7831950800000413
    - 6W4L2
      - /May22/6W4L2/
      - relaxed scf finished
        cuh2o6l42=-667.06330550
        cuh2o6l42-singlecu2-singleh2o*6
        -0.8521010599999954
  - reference https://pubs.acs.org/doi/abs/10.1021/jp1000804
CuCl(H2O)5
- replace one h2o from 6W4L2
- /May23/5W1Cl
  - relaxed scf finished
    - cuclh2o5=-658.25247725
      - cuclh2o5-singlecu2-singlecl-singleh2o*5
        -1.1932985299999928
- reference https://pubs.acs.org/doi/abs/10.1021/jp1000804
CuCl2(H2O)4
- replace two h2o form 6W4L1
- /May23/4W2Cl
  - relased scf finished
    - cucl2h2o4=-649.32743653
      - cucl2h2o4-singlecu2-singlecl2-singleh2o4
        -1.4202835300000345
- reference https://pubs.acs.org/doi/10.1021/jp909092p
Cu(I) chloride
- CuCl
  - without water /May25/0W1Cl+1
    - relaxing
    - scf finished
      - cucl=-438.29948177
        cucl-singlecu1-singlecl
        -0.3386133099999924
  - may have 1 water molecule /May25/1W1Cl+1
    - relaxing
    - scf finished
      - cuclh2o=-482.42694170
        cuclh2o-singlecu1-singlecl-singleh2o
        -0.42453573999998184
  - reference https://doi.org/10.1016/S0009-2614(00)01110-6
- CuCl2 -
  - /May23/0W2Cl+1
    - relaxed scf finished
      - cucl2=-473.36700849
        cucl2-singlecu1-singlecl*2
        -0.5166282499999824
  - reference https://doi.org/10.1016/S0009-2614(00)01110-6
- CuCl3 2- at 25 C is found but with very weak bonded Cl-, at high Cl- concentration
- reference: https://doi.org/10.1016/j.gca.2006.09.015
- https://doi.org/10.1021/acs.analchem.5b00052
  - this paper pointed out, for Cu chloride, whatever valence, coordination number with Cl- increased with increasing Cl- ion concentration in solvation, predicted the existence of Cu(I)Cl3 2- even at low concentration.
  - but my calculation cant predict the structure of Cu(I)Cl3 2-, this paper also not considered the structure but only the reaction
- https://doi.org/10.1016/j.gca.2012.10.027
  - Fig. 11
    - CuCl2 to CuCl3 at room temperature, log K < 0, not that stable
- https://doi.org/10.1016/j.gca.2006.09.015
  - Fig .1 from reference
    - CuCl3 dominate only at high Cl concentration, low pH (<9)
Cl(H2O)6
- /May25/Cl6W-1/
  - relaxed scf finished
    - clh2o6=-299.28590227
      - clh2o6-singlecl-singleh2o*6
        -0.14716549000002033
- reference https://doi.org/10.1039/C3CP50652E
  - chloride ion prefer coordinated with six water molecules, symmetrically H-bonding
  - essential degeneracy between water-water and water-Cl H-bonding, strong similarity in the water and chloride electronic structure
- reference https://doi.org/10.1080/00268976.2015.1059959
  - PBE vdW XC AIMD, sixfold Cl-O coordination is dominated, in the first solvation shell surrounding the Cl- ion
  - O-Cl-O angular distribution showing $theta\approx 75 \degree$, indicating distorted trigonal prismatic structures

2025-05-26

energy diagram drawing

atomic model

/May26

results

atomic model
free energy (formation energy differnece)
- cuh2o6l5
- cuh2o6l41
- cuclh2o5
- cucl2h2o4
- cu(I)cl
- cucl(I)h2o
- cu(I)cl2
Win11: Desktop/Cuion/model-2025May26/results_2025May26

doing:

Cl(H2O)6

not yet done:

3W2Cl
- modeling
4W1Cl1
4W1Cl2
5W5L

2025-05-27

doing:

Cl(H2O)6
- relaxing
3W2Cl
- relaxing
4W1Cl1
- relaxing
4W1Cl2
- relaxing
5W5L
- relaxing
methods
SI
- graphing

Results

singleatom

singlecu2=-401.96197944 singlecu1=-403.07135668 singlecl=-34.88951178 singleh2o=-44.04153750

Cu2+

5L

3W2Cl
- [CuCl2(H2O)3]0
- cucl2h2o3=-605.21675997
- cucl2h2o3-singlecu2-singlecl*2-singleh2o*3
- -1.3511444700000368
- -18.38326632
4W1Cl1
- [CuCl(H2O)4]1+
- cuclh2o4l1=-614.15869898
- cuclh2o4l1-singlecu2-singlecl-singleh2o*4
- -1.1410577600000806
- -15.52488957
4W1Cl2
- [CuCl(H2O)4]1+
- cuclh2o4l2=-614.13798055
- cuclh2o4l2-singlecu2-singlecl-singleh2o*4
- -1.1203393299999789
- -15.24300082
5W5L
- [Cu(H2O)5]2+
- cuh2o5=-622.85887760
- cuh2o5-singlecu2-singleh2o*5
- -0.6892106600000432
- -9.377193477

6L

4W2Cl1
- [CuCl2(H2O)4]0
- cucl2h2o41=-649.32743653
- cucl2h2o41-singlecu2-singlecl*2-singleh2o*4
- -1.4202835300000345
- -19.32395162
4W2Cl2
- [CuCl2(H2O)4]0
- cucl2h2o42=-649.31965224
- cucl2h2o42-singlecu2-singlecl*2-singleh2o*4
- -1.4124992400000167
- -19.21804090966823
5W1Cl
- [CuCl(H2O)5]1+
- cuclh2o5=-658.25247725
- cuclh2o5-singlecu2-singlecl-singleh2o*5
- -1.1932985299999928
- -16.23566181
6W4L1
- [Cu(H2O)6]2+
- cuh2o6l41=-666.99439952
- cuh2o6l41-singlecu2-singleh2o*6
- -0.7831950800000413
- -10.6559173
6W4L2
- [Cu(H2O)6]2+
- cuh2o6l42=-667.06330550
- cuh2o6l42-singlecu2-singleh2o*6
- -0.8521010599999954
- -11.59343139
6W5L
- [Cu(H2O)6]2+
- cuh2o6l5=-667.01612658
- cuh2o6l5-singlecu2-singleh2o*6
- -0.8049221400000306
- -10.95152916

Cu1+

0W1Cl+1
- [CuCl]0
- cucl=-438.29948177
- cucl-singlecu1-singlecl
- -0.3386133099999924
- -4.607071112
1W1Cl+1
- [CuClH2O]0
- cuclh2o=-482.42694170
- cuclh2o-singlecu1-singlecl-singleh2o
- -0.42453573999998184
- -5.776105918
0W2Cl+1
- [CuCl2]1-
- cucl2=-473.36700849
- cucl2-singlecu1-singlecl*2
- -0.5166282499999824
- -7.029088981

Cl-1

Cl6W-1
- [Cl(H2O)6]1-
- clh2o6=-299.28590227
- clh2o6-singlecl-singleh2o*6
- -0.14716549000002033
- -2.002289507

Reference

2+ CuH2O and CuClH2O different configuration
- reference https://pubs.acs.org/doi/abs/10.1021/jp1000804
2+ CuCl2H2O different configuration
- reference https://pubs.acs.org/doi/10.1021/jp909092p
DFT calculation MIT Chem
- https://doi.org/10.1021/acs.jpclett.2c01026
- B3LYP
- single point
1+ Cu
- XAFS 2000
  - https://doi.org/10.1016/S0009-2614(00)01110-6
  - Cu1+ linear monochloro and dichloro species
  - no observes of chloride with higher coordination
- AIMD 2007 Sherman
  - https://doi.org/10.1016/j.gca.2006.09.015
  - predict CuCl3 and CuCl4 at high concentration
- AIMD 2013 Mei
  - https://doi.org/10.1016/j.gca.2012.10.027
  - low formation constant of CuCl3
- XAS 2007 Brugger
  - https://doi.org/10.1016/j.gca.2007.08.003
  - only at very high concentration
- Raman 2013 Applegarth
  - https://doi.org/10.1021/jp406580q
  - CuCl3 only at very high concentration
  - dft predicted linear
  - but dft can predict CuCl3 structure
Cl-
- reference https://doi.org/10.1039/C3CP50652E
  - chloride ion prefer coordinated with six water molecules, symmetrically H-bonding
  - essential degeneracy between water-water and water-Cl H-bonding, strong similarity in the water and chloride electronic structure
- reference https://doi.org/10.1080/00268976.2015.1059959
  - PBE vdW XC AIMD, sixfold Cl-O coordination is dominated, in the first solvation shell surrounding the Cl- ion
  - O-Cl-O angular distribution showing $theta\approx 75 \degree$, indicating distorted trigonal prismatic structures
    2025-06-03
    ADF in AMS
Task - Geometry Optimization
Frequencies - Yes
Total charge
Unrestricted - Yes
XC functional - Hybrid:B3LYP
Basis set - QZ4P
Frozen core - None
Numerical quality - Normal
Properties
- Thermodynamics
  - Pressure - 1.0 atm
  - Temperatures - 298.15 K

can get

Entropy (cal/mol-K)
Energy from Engine (eV)
Internal Energy U (eV)
Gibbs free energy (eV)
6W4L1
Entropy (cal/mol-K)
- 119.220
Energy from Engine (eV)
- -89.2638
Internal Energy U (eV)
- -84.7040
Gibbs free energy (eV)
- -86.2197

5W1Cl

Entropy (cal/mol-K)
- 126.074
Energy from Engine (eV)
- -85.9135
Internal Energy U (eV)
- -82.0349
Gibbs free energy (eV)
- -83.6392

4W2Cl

Entropy (cal/mol-K)
- 115.666
Energy from Engine (eV)
- -78.9343
Internal Energy U (eV)
- -75.7699
Gibbs free energy (eV)
- -77.2396

0W1Cl+1

Entropy (cal/mol-K)
- 56.645
Energy from Engine (eV)
- -5.3202
Internal Energy U (eV)
- -5.2226
Gibbs free energy (eV)
- -5.9292

1W1Cl+1

Entropy (cal/mol-K)
- 72.495
Energy from Engine (eV)
- -23.6026
Internal Energy U (eV)
- -22.7601
Gibbs free energy (eV)
- -23.6717

0W2Cl+1

Entropy (cal/mol-K)
- 68.008
Energy from Engine (eV)
- -13.2151
Internal Energy U (eV)
- -13.0357
Gibbs free energy (eV)
- -13.8893