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Re: Analysis of ETS-NOCV results

dummy@example.com (saeed_E) — Tue, 20 Feb 2024 15:48:15 +0000

Dear Tian,
Thank you very very much for the valuable time you kindly assigned to answer my questions.
Please let me state that, this afternoon, I sent to you an email including an ETS-NOCV analysis and, most importantly, corresponding interpretation. I would be highly grateful if you so kindly have a look at this document and let me know your determining comments so that I can deeply understand the concepts of ETS-NOCV. It seems provided explanations to be correct and I found reasonable solution based on the chemical concepts but, as always, I extremely need your very valuable confirmation to avoid any misunderstanding and wrong usage in manuscript.
Please let me say that this document would not take your valuable time by more than five minutes.

Sincerely yours,
Saeed

Re: Analysis of ETS-NOCV results

dummy@example.com (sobereva) — Tue, 20 Feb 2024 13:44:39 +0000

NOCV orbitals are obtained as eigenvectors of delta-P matrix (see Section 3.26 of Multiwfn manual for underlying theory), there is no directly relationship between NOCVs and fragment orbitals.

The only way of deriving the relationship between the two kinds of orbitals is using subfunction 6 of main function 200 of Multiwfn, see Section 3.200.6 of Multiwfn manual for detail. This function is able to calculate contribution of an orbital to another orbital.

Re: Analysis of ETS-NOCV results

dummy@example.com (saeed_E) — Mon, 19 Feb 2024 14:09:54 +0000

Dear Tian,
I could finally attach these files as screenshot. Please accept my apology for successive messages. As you can see, the figures were respectfully attached. I want to know which fragment orbitals are actually involved in NOCV pairs 1 and 2 whose delta_RHO isosurfaces (resulting from fragment orbitals interactions) are presented.

Sincerely,
Saeed

Re: Analysis of ETS-NOCV results

dummy@example.com (saeed_E) — Mon, 19 Feb 2024 13:22:54 +0000

While I tried several times using the way you mentioned, no images could be uploaded. The figures were "tag" and changed them to "png" and "jpg" but any tries were unsuccessful!
While the uploading process is completed 100%, at the end, I receive the message indicating no image can successfully uploaded!

Re: Analysis of ETS-NOCV results

dummy@example.com (sobereva) — Mon, 19 Feb 2024 13:15:13 +0000

I cannot view you figures. Please use "Add image to post" button to upload images.

Re: Analysis of ETS-NOCV results

dummy@example.com (saeed_E) — Mon, 19 Feb 2024 13:12:47 +0000

Dear Tian,
Your kind attention is appreciated,
Attached are the results and two figures for NOCV pairs 1 and 2 (with largest contribution). Please note that the structure is a TS associated with 1,3-DC reaction between CH2=NH-O (simplest nitrone) and CH2=C(Me)2. Please let me know which fragment orbitals are involved in the ESTNOCV 1 and 2.

Sincerely,
Saeed

Results:

Pair Energy | Orbital Eigenvalue Energy | Orbital Eigenvalue Energy
1 -42.50 1 0.63844 -104.62 160 -0.63844 -38.05
2 -30.83 2 0.47130 -79.36 159 -0.47130 -13.94
3 -1.11 3 0.05944 -34.23 158 -0.05944 -15.63
4 -1.15 4 0.05691 54.10 157 -0.05691 74.34
5 -0.57 5 0.04260 -40.33 156 -0.04260 -26.95
6 -0.45 6 0.03859 -83.44 155 -0.03859 -71.69
7 -0.38 7 0.03176 15.09 154 -0.03176 27.11
8 -0.30 8 0.03068 8.71 153 -0.03068 18.36
9 -0.25 9 0.02829 -21.33 152 -0.02829 -12.54
10 -0.22 10 0.02455 13.63 151 -0.02455 22.47
11 -0.16 11 0.02163 19.87 150 -0.02163 27.10
12 -0.15 12 0.02028 39.74 149 -0.02028 47.11
13 -0.15 13 0.01844 -17.38 148 -0.01844 -9.45
14 -0.10 14 0.01616 70.28 147 -0.01616 76.20
15 -0.09 15 0.01365 72.11 146 -0.01365 78.84
16 -0.07 16 0.01186 70.61 145 -0.01186 76.35
17 -0.07 17 0.01041 72.17 144 -0.01041 79.22
18 -0.05 18 0.00997 51.20 143 -0.00997 56.24
19 -0.05 19 0.00873 144.76 142 -0.00873 150.00
20 -0.01 20 0.00412 -227.20 141 -0.00412 -223.75
21 -0.01 21 0.00286 22.46 140 -0.00286 24.31
22 -0.01 22 0.00170 -2515.20 139 -0.00170 -2509.27
23 -0.01 23 0.00144 -2772.50 138 -0.00144 -2766.95
Sum of NOCV eigenvalues: 0.00000
Sum of pair energies: -78.67 kcal/mol

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Re: Analysis of ETS-NOCV results

dummy@example.com (sobereva) — Mon, 19 Feb 2024 09:21:35 +0000

Without figures of a practical system I can hardly answer this question

Analysis of ETS-NOCV results

dummy@example.com (saeed_E) — Sun, 18 Feb 2024 14:23:49 +0000

Dear Tian,

The NOCV pairs contribution, associated with orbitals interaction between two interacting fragments, could nicely be portrayed using the EST-NOCV analysis. In this sense, various contributions are depicted with corresponding NOCV pair energy and eigenvalue. In most cases, we need to visualize a pair interaction to distinguish which orbitals interaction is involved. For instance, the largest contribution in an intermolecular hydrogen bonding interaction corresponds to the electron density shift from the lone pair of electron donor toward the sigma anti bonding of the electron acceptor, lp-->sigma*. But, there are some cases in which interpretation becomes so difficult and one cannot easily characterize which orbital pairs are involved. Indeed, through visualization of an ETS-NOCV pair, it may be not clear that a given ETS-NOCV pair is associated with a lp-->pi* or a pi--->pi* and so on. Please let me know what solution you recommend in such cases.

Sincerely,
Saeed