Multiwfn forum

Dear all,

Recently, I have started running some simple tests with Multiwfn 3.8 to analyse hole-electrons formation in small gold clusters. I run default TD-DFT (TDA) calculations on Orca 5.03 and these inicial tests used B3LYP functional in combination with LANL2DZ. I am mainly interested in MO, atoms, and basis function contributions to hole-electrons distribution. However, for some of the contributions given by Multiwfn 3.8, I get negative percentages. For example:

Using atom contribution from Mulliken method:
Contribution of each non-hydrogen atom to hole and electron:
1(Au) Hole: 6.66 % Electron: 1.59 % Overlap: 3.26 % Diff.: -5.07 %
2(Au) Hole: 1.89 % Electron: -0.46 % Overlap: 0.00 % Diff.: -2.36 %
3(Au) Hole: 2.73 % Electron: 2.12 % Overlap: 2.41 % Diff.: -0.61 %
4(Au) Hole: -7.83 % Electron: 0.51 % Overlap: 0.00 % Diff.: 8.34 %
5(Au) Hole: 5.14 % Electron: 7.69 % Overlap: 6.29 % Diff.: 2.55 %

Or for basis function contributions:
Sum of hole contributions: 0.921316
Sum of electron contributions: 0.921316

Basis Type Atom Shell Hole Electron Overlap Diff.
3 S 1(Au) 3 2.15 % 0.21 % 0.67 % -1.94 %
11 Y 1(Au) 6 1.04 % 0.03 % 0.18 % -1.01 %
34 Z 2(Au) 14 -1.29 % -0.02 % 0.00 % 1.27 %
55 Y 3(Au) 22 0.11 % 1.12 % 0.35 % 1.01 %
76 X 4(Au) 30 -0.72 % -1.77 % 0.00 % -1.05 %
77 Y 4(Au) 30 -6.11 % -0.10 % 0.00 % 6.01 %

I was wondering what could be the origin of this negative percentages and if this could indicate a problem with my TD-DFT calculation. Would this indicate that other contributions that are all positive (atom contribution from Hirshfeld partition method and MO contributions) could be wrong?

Many thanks,
Maicon