Exploring the Interaction Natures in Plutonyl (VI) Complexes with Topological Analyses of Electron Density
Abstract
:1. Introduction
2. Computational Details
3. Results and Discussion
3.1. Structures in Gaseous and Solution Phases
3.2. Natural Bonding Orbital Analyses
3.3. QTAIM Topological Analyses
3.4. Interaction Quantum Atom (IQA) Analyses
3.5. Electron Localization Function (ELF) Analyses
3.6. Noncovalent Interaction (NCI) Analyses
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Species | Gas | Solution | Expt | |||
---|---|---|---|---|---|---|
Pu–Oyl | Pu–OH2 | Pu–Oyl | Pu–OH2 | Pu–Oyl | Pu–OH2 | |
1.711(1.673) | 1.716(1.723) | |||||
PuO2(H2O | 1.751(1.703) | 2.451(2.467) | 1.763(1.716) | 2.402(2.449) | 1.74 | 2.41 |
1.748(1.714) | 1.771(1.785) | |||||
PuO2(H2O | 1.808(1.766) | 2.539(2.591) | 1.832(1.779) | 2.497(2.597) | 1.81 | 2.47 |
Species | Gas | Solution | ||||
---|---|---|---|---|---|---|
Pu–Oyl | Pu–L | Pu–OH2 | Pu–Oyl | Pu–L | Pu–OH2 | |
PuO2 | 1.811(1.773) | 2.222(2.225) | 1.806(1.766) | 2.201(2.209) | ||
PuO2 | 1.772(1.742) | 2.749(2.743) | 1.775(1.737) | 2.706(2.692) | ||
PuO2Cl2(H2O)2 | ||||||
Cis- | 1.768(1.729) | 2.612(2.582) | 2.445(2.513) | 1.768(1.732) | 2.671(2.664) | 2.345(2.476) |
Trans- | 1.767(1.729) | 2.623(2.591) | 2.417(2.481) | 1.768(1.728) | 2.670(2.640) | 2.349(2.421) |
PuO2Cl2(H2O)3 | ||||||
Cis- | 1.767(1.725) | 2.665(2.619) | 2.574(2.624) | 1.771(1.729) | 2.738(2.680) | 2.458(2.556) |
Trans- | 1.767(1.722) | 2.717(2.661) | 2.490(2.558) | 1.771(1.728) | 2.757(2.703) | 2.441(2.523) |
Expt | 1.75 | 2.70 | 2.49 | |||
PuO2Cl(H2O | 1.763(1.723) | 2.617(2.566) | 2.493(2.542) | 1.768(1.719) | 2.722(2.634) | 2.424(2.486) |
Expt | 1.75 | 2.75 | 2.43 | |||
PuO2 | 1.770(1.732) | 2.907(2.904) | 1.776(1.736) | 2.853(2.862) | ||
PuO2(OH | 1.859(1.798) | 2.281(2.288) | 1.836(1.791) | 2.243(2.272) | ||
PuO2(OH)2(H2O)3 | 1.836(1.742) | 2.267(2.199) | 2.548(2.611) | 1.800(1.755) | 2.193(2.201) | 2.523(2.588) |
PuO2(O)2(H2O)3 | 1.827(1.788) | 2.398(2.379) | 2.526(2.595) | 1.838(1.796) | 2.444(2.411) | 2.471(2.563) |
PuO2(NO3 | 1.762(1.729) | 2.500(2.493) | 1.761(1.737) | 2.493(2.485) | ||
PuO2(NO3)2(H2O)2 | 1.767(1.722) | 2.483(2.474) | 2.466(2.524) | 1.770(1.730) | 2.512(2.490) | 2.434(2.505) |
Expt | 1.727 | 2.432 | 2.497 | |||
PuO2(CO3 | 1.815(1.784) | 2.558(2.544) | 1.809(1.780) | 2.467(2.469) | ||
PuO2(CO3)(H2O)3 | 1.814(1.773) | 2.620(2.607) | 2.514(2.581) | 1.825(1.781) | 2.678(2.673) | 2.456(2.536) |
Species | q | q | q | EC | EC | EC | WBI | WBI |
---|---|---|---|---|---|---|---|---|
(Pu) | (Oyl) | (L) | (Pu) | (Oyl) | (L) | (Pu=O) | (Pu–L) | |
2.04 | −0.52 | – | – | 2.05 | – | |||
2.50 | −0.25 | – | – | 2.24 | – | |||
PuO2(H2O | 1.44 | −0.54 | −0.89 | 2.07 | (0.24) a | |||
PuO2(H2O | 1.44 | −0.26 | −0.85 | 2.29 | (0.39) | |||
PuO2 | 1.39 | −0.46 | −0.62 | 2.10 | 0.65 | |||
PuO2 | 0.68 | −0.39 | −0.48 | 2.18 | 0.86 | |||
PuO2Cl2(H2O)2 | ||||||||
Cis- | 0.86 | −0.35 | −0.28 | 2.23 | 1.14/(0.35) | |||
Trans- | 0.86 | −0.35 | −0.27 | 2.22 | 1.14/(0.35) | |||
PuO2Cl2(H2O)3 | ||||||||
Cis- | 0.81 | −0.34 | −0.3 | 2.23 | 1.08/(0.29) | |||
Trans- | 0.85 | −0.34 | −0.36 | 2.23 | 1.01/(0.31) | |||
PuO2Cl(H2O | 1.09 | −0.32 | −0.18 | 2.25 | 1.26/(0.32) | |||
PuO2 | 0.57 | −0.40 | −0.44 | 2.18 | 0.89 | |||
PuO2(OH | 1.07 | −0.51 | −0.94 | 2.08 | 0.79 | |||
PuO2(OH)2(H2O)3 | 1.13 | −0.37 | −0.86 | 2.21 | 0.95/(0.26) | |||
PuO2(O)2(H2O)3 | 1.31 | −0.54 | −0.31 | 2.07 | 0.40/(0.24) | |||
PuO2(NO3 | 1.13 | −0.32 | −0.42 | 2.22 | 0.41 | |||
PuO2(NO3)2(H2O)2 | 1.15 | −0.32 | −0.44 | 2.24 | 0.43/(0.32) | |||
PuO2(CO3 | 1.22 | −0.52 | −0.73 | 2.06 | 0.41 | |||
PuO2(CO3)(H2O)3 | 1.40 | −0.55 | −0.68 | 2.06 | 0.25/(0.25) |
Pu-L BCPs | |||||
---|---|---|---|---|---|
Species | (Pu,L) | ||||
0.334 | 0.263 | −0.322 | 2.181 | 1.90 | |
0.376 | 0.349 | −0.393 | 2.374 | 1.88 | |
PuO2(H2O | 0.035 | 0.150 | 0.002 | 0.204 | 0.95 |
PuO2(H2O | 0.049 | 0.209 | 4.8 × | 0.299 | 0.99 |
PuO2 | 0.081 | 0.363 | −0.005 | 0.578 | 1.05 |
PuO2 | 0.050 | 0.113 | −0.008 | 0.577 | 1.21 |
PuO2Cl2(H2O)2 | |||||
Cis- | 0.071 (0.045) | 0.156 (0.184) | −0.016 (3.6 × ) | 0.822 (0.287) | 1.30 |
Trans- | 0.070 (0.047) | 0.143 (0.204) | −0.016 (6.2 × ) | 0.823 (0.290) | 1.31 |
PuO2Cl2(H2O)3 | |||||
Cis- | 0.066 (0.036) | 0.143 (0.131) | −0.014 (3.2 × ) | 0.742 (0.230) | 1.28 |
Trans- | 0.061 (0.045) | 0.132 (0.181) | −0.012 (3.8 × ) | 0.673 (0.266) | 1.26 |
PuO2Cl(H2O | 0.074 (0.045) | 0.156 (0.180) | -0.018 (2.1 × ) | 0.927 (0.281) | 1.31 |
PuO2 | 0.044 | 0.082 | −0.007 | 0.589 | 1.25 |
PuO2(OH | 0.082 | 0.283 | −0.011 | 0.666 | 1.14 |
PuO2(OH)2(H2O)3 | 0.105 (0.036) | 0.360 (0.136) | −0.022 (3.5 × ) | 0.827 (0.213) | 1.20 |
PuO2(O)2(H2O)3 | 0.061 (0.034) | 0.241 (0.156) | −0.004 (0.002) | 0.387 (0.211) | 1.06 |
PuO2(NO3 | 0.051 | 0.185 | −0.002 | 0.324 | 1.04 |
PuO2(NO3)2(H2O)2 | 0.054 (0.044) | 0.188 (0.176) | −0.003 (6.0 | 0.349 (0.247) | 1.05 |
PuO2(CO3 | 0.050 | 0.158 | −0.002 | 0.370 | 1.06 |
PuO2(CO3)(H2O)3 | 0.037 (0.037) | 0.143 (0.155) | 1.7 × (8.1 × ) | 0.228 (0.240) | 0.99 |
Complexes | Atoms | / | |||||||
---|---|---|---|---|---|---|---|---|---|
(a.u) | (a.u) | (a.u) | (a.u) | (kcal/mol) | (kcal/mol) | (kcal/mol) | |||
PuO2(H2O | Pu–O(H2O) | −66.39 | −53.69 | 58.35 | 61.09 | −402.23 | −39.53 | −441.77 | 0.09 |
PuO2 | Pu–F | −78.60 | −66.90 | 72.76 | 72.27 | −293.67 | −74.05 | −367.72 | 0.20 |
PuO2 | Pu–Cl | −115.93 | −103.53 | 111.48 | 107.66 | −199.55 | −59.61 | −259.16 | 0.23 |
PuO2 | Pu–Br | −220.93 | −201.90 | 216.87 | 205.69 | −176.96 | −56.48 | −233.43 | 0.24 |
PuO2(OH | Pu–O(OH−) | −71.53 | −58.09 | 62.90 | 66.07 | −412.27 | −81.58 | −493.85 | 0.17 |
PuO2(O)2(H2O)3 | Pu–O() | −63.33 | −56.27 | 60.51 | 58.90 | −123.62 | −46.44 | −170.06 | 0.27 |
PuO2(NO3 | Pu–O() | −61.93 | −53.36 | 57.74 | 57.23 | −198.92 | −39.53 | −238.45 | 0.17 |
Pu–N() | −37.68 | −39.63 | 42.89 | 34.82 | 247.87 | −1.88 | 245.98 | −0.008 | |
PuO2(CO3 | Pu–O() | −64.34 | −51.98 | 56.21 | 59.50 | −384.04 | −38.91 | −422.94 | 0.09 |
Pu–C() | −23.43 | −33.31 | 36.03 | 21.66 | 596.13 | −1.26 | 594.88 | −0.002 |
Complexes | ||
---|---|---|
PuO2(H2O | 0.604 | 0.122 |
PuO2 | 0.579 | 0.172 |
PuO2 | 0.593 | 0.229 |
PuO2 | 0.597 | 0.247 |
PuO2(OH | 0.567 | 0.227 |
PuO2(O)2(H2O)3 | 0.581 | 0.153 |
PuO2(NO3 | 0.576 | 0.166 |
PuO2(CO3 | 0.594 | 0.152 |
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Du, J.; Sun, X.; Jiang, G. Exploring the Interaction Natures in Plutonyl (VI) Complexes with Topological Analyses of Electron Density. Int. J. Mol. Sci. 2016, 17, 414. https://doi.org/10.3390/ijms17040414
Du J, Sun X, Jiang G. Exploring the Interaction Natures in Plutonyl (VI) Complexes with Topological Analyses of Electron Density. International Journal of Molecular Sciences. 2016; 17(4):414. https://doi.org/10.3390/ijms17040414
Chicago/Turabian StyleDu, Jiguang, Xiyuan Sun, and Gang Jiang. 2016. "Exploring the Interaction Natures in Plutonyl (VI) Complexes with Topological Analyses of Electron Density" International Journal of Molecular Sciences 17, no. 4: 414. https://doi.org/10.3390/ijms17040414