CDA of three fragments, negative (-) donation / back-donation

sdmultiwfn · 2022-12-08 11:08:10

I have a metal carbonyl complex (Ligand)Fe(2+)(CO)2. I followed the tutorial in the manuscript for the CDA of (Cl)2Pt(NH3)2, so I calculated the fragments L, (CO)2 and Fe2+.

The result of the CDA (option 16) for d is: Fe2+ -> (CO)2 0.057 e and for b: (CO)2 -> Fe2+ -0.529 e, if the order is Fe(CO)2L (Fe2+ is the first and L the last fragment: fragments 1,2). When I change the order to (CO)2LFe I get: d: (CO)2 -> Fe2+ -0.529 and b: Fe2+ -> (CO)2 0.057 (fragments 1,3), which is the same result.

My problem is, that I don't understand the negative (-) sign. I would understand if 0.529 electrons are donated from CO to Fe2+ and 0.057 e are back donated from Fe2+ to CO. Can anyone help? Thank you in advance.

sobereva · 2022-12-08 21:16:40

Please upload your relevant files (input files of your quantum chemistry program, and wavefunction files) to netdisk and paste downloading link here, or directly send them to my E-mail. I will check sanity of your files.

sdmultiwfn · 2022-12-09 08:09:02

Thank you very much!

I have sent you a link to the files via email.

sobereva · 2022-12-12 08:27:01

I have checked your file, two suggestions:

(1) Use def2-SVP instead of def2-TZVP and check if the result becomes more resonable. Def2-SVP shows lower diffuse character than def2-TZVP, while CDA doesn't work well if diffuse character of the basis set is evident. However, according to my experience, CDA should be compatible with def2-TZVP.

(2) Try different partitioning of fragments. Currently a single Fe atom was defined as a fragment, however, in this case the occupancy of d atomic-orbitals is arbitrary. You can load Fe.molden.input into Multiwfn and use main function 0 to check which d orbitals are occupied. This evident arbitrariness affects CDA result and may lead d and b terms lack of meaning. So, when studying interaction between Fe and a ligand, I suggest defining Fe along with one or more other ligands as a single fragment, then occupancy of d-orbitals will not be arbitrary and it is expected that the result will be more reasonable.

sdmultiwfn · 2022-12-12 15:06:16

Thank your very much! I will check your suggestions.

Multiwfn forum

#1 2022-12-08 11:08:10

CDA of three fragments, negative (-) donation / back-donation

#2 2022-12-08 21:16:40

Re: CDA of three fragments, negative (-) donation / back-donation

#3 2022-12-09 08:09:02

Re: CDA of three fragments, negative (-) donation / back-donation

#4 2022-12-12 08:27:01

Re: CDA of three fragments, negative (-) donation / back-donation

#5 2022-12-12 15:06:16

Re: CDA of three fragments, negative (-) donation / back-donation

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