Fukui Functions and the Dual Descriptor¶

Chemical reactivity can be analyzed using Fukui Functions and the Dual Descriptor. ADF provides the tools to perform this analysis. The local chemical reactivity can be described per atom via a condensed Fukui Function. Subsequently, the local softness can be determined as well. The Fukui Functions and the Dual Descriptor can be visualized in the GUI with AMSview.

Step 1: Setting up the calculation¶

Start AMSinput with the panel active.

Build the carbon monoxide molecule using the search function

Set the XC functional to GGA BP86

Set Relativity → None (not all options of QTAIM analysis can be performed in combination with relativistic effects)

Open the Conceptual DFT tab in Properties → Conceptual DFT

Check both Fukui options at the bottom of the panel (nucleophilic and electrophilic attack)

Here you can specify which Fukui functions you want to calculate. Both can be calculated at the same time, and is also required for the Dual Descriptor. The default way to calculate the Fukui functions is to add or subtract a whole electron. However, it is possible to use fractional charges by modifying the Charge change parameter.

Open the Bader tab in Properties → QTAIM

Check the Perform QTAIM analysis button

Set the Analysis level to Full

The condensed Fukui Functions and local softness are calculated using atomic charges. By default the Hirshfeld, Voronoi and Mulliken charges are used. The Bader charges can be used as well if they are calculated.

Use File → Save As to save the file as ‘CO_Fukui’

Run the calculation

Hirshfeld Partitioning


MAIN ATOMIC DESCRIPTORS: CANONICAL ENSEMBLE
===========================================

Atom   f+     f-     f0     f(2)
C(1)   0.670  0.674  0.672  -0.004
O(2)   0.330  0.326  0.328  0.004
-------------------------------------
Total  1.000  1.000  1.000  -0.000

Step 3: Visualizing the Fukui functions and Dual Descriptor¶

The Fukui functions can be visualized in AMSview, using the electron density.

SCM → View

Set the grid size to medium Fields → Grid → Medium

Add an isosurface with phase Add → Isosurface: With Phase

At the bottom of the screen (in Select Field…) choose the Properties → Fukui Plus

The instruction on the screen asks for the result file of the Fukui Plus calculation

Choose adf.plus.rkf

Enable the second checkbox for the field to use the wireframe model

AMSview will create some calculated fields to combine the spin densities for the unrestricted calculations, and calculates the Fukui plus function. The wireframe model allows us to see any hidden isosurface. Another way to do this is by lowering the opacity in the field details.

Disable the field by unchecking the first checkbox at the bottom

Create a new isosurface with phase

At the bottom of the screen (in “Select Field…”) choose Properties → Dual Descriptor (FDL)

The fukui plus function is already loaded, the instruction now asks for the missing Fukui Minus calculation

Choose adf.minus.rkf

Enable the second checkbox for the field to use the wireframe model