NBO/NRT Two-State Theory of Bond-Shift Spectral Excitation
Abstract
:1. Introduction
- (1)
- Natural bond orbital (NBO) [10,11] donor-acceptor interaction that transfers two electrons from a Lewis-type (L; formally occupied) NBO of the parent natural Lewis-structure (NLS) bonding pattern (e.g., amide nitrogen lone pair, nN) to a non-Lewis (NL; formally vacant) NBO (e.g., adjacent carbonyl pi-antibond, π*CO);
- (2)
- Robinson-type “curly arrow” depiction [12] of vicinal π-type delocalization, leading to πCO → πCN bond shift, with concomitant nn → nO lone pair shift and charge transfer;
- (3)
- Resonance-structural depiction of the secondary bonding pattern that results from the e-pair bond shift in the parent NLS.
2. NBO/NRT Deletion Tools for Describing Resonance Delocalization
3. Diabatic Two-State Model of Resonance Mixing
4. Chemical Applications
4.1. Methods
4.2. SN2 Fluoride Exchange Reaction
4.3. Polyene Bond Shifts of Cyanine Dyes
5. Concluding Discussion
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Not available. |
Resonance Structure | I | II |
---|---|---|
(i) reactivity | reactant (R) | product (P) |
(ii) spectroscopy | ground-state (g.s.) | excited state (x.s.) |
(iii) single-determinant wavefunction | ΨI(SD) | ΨII(SD) |
(iv) NBO configuration type | NLS | 2e L→NL excitation |
Method | HF | B3LYP | CAM-B3LYP | M06 | wB97XD |
---|---|---|---|---|---|
ΔE(2 − st) | 160 | 171 | 162 | 169 | 158 |
ΔE(CIS/TD) | 213 | 214 | 228 | 208 | 230 |
(a) nN→πCC* | n = 2 | n = 3 | n = 4 | n = 5 |
ΔEDA(2) | 60.85 | 57.74 | 55.77 | 54.34 |
ΔEDA($DEL) | 64.71 | 61.71 | 59.88 | 58.97 |
(b) πCC→πCN* | ||||
ΔEDA(2) | 58.53 | 60.42 | 61.73 | 62.88 |
ΔEDA($DEL) | 67.14 | 66.30 | 64.99 | 64.14 |
(c) πCC→πCC* | ||||
ΔEDA(2) | 35.04 | 34.68 30.93 | 29.06 30.48 34.90 | 27.95 27.20 29.00 35.87 |
ΔEDA($DEL) | 41.83 | 36.56 35.96 | 33.80 31.09 33.39 | 33.22 27.54 26.53 31.80 |
δn(av) | 57.89 | 50.13 | 44.63 | 40.37 |
n | 2 | 3 | 4 | 5 |
---|---|---|---|---|
Δℇ(n)(2 − st) | 115.78 | 100.26 | 89.26 | 80.74 |
Δℇ(n)(TD) | 94.81 | 79.38 | 68.79 | 61.07 |
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Jiao, Y.; Weinhold, F. NBO/NRT Two-State Theory of Bond-Shift Spectral Excitation. Molecules 2020, 25, 4052. https://doi.org/10.3390/molecules25184052
Jiao Y, Weinhold F. NBO/NRT Two-State Theory of Bond-Shift Spectral Excitation. Molecules. 2020; 25(18):4052. https://doi.org/10.3390/molecules25184052
Chicago/Turabian StyleJiao, Yinchun, and Frank Weinhold. 2020. "NBO/NRT Two-State Theory of Bond-Shift Spectral Excitation" Molecules 25, no. 18: 4052. https://doi.org/10.3390/molecules25184052