Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers
Abstract
:1. Introduction
2. Results and Discussion
2.1. Molecular Geometry of Selected PBDEs
2.1.1. Comparison of Calculated Structural Parameters with Experimental Values for PBDEs
2.1.2. The Comparison of Structural Parameters between Neutral and Anionic Species of the Selected PBDEs
2.2. Electron Affinities (EA) of the Selected PBDEs
2.3. The Possible Anionic States and the Orbital Energies for the Selected BDE Congeners
2.4. Use of Optimized Geometries of BDE Congeners to Predict the Dominant Debromimation Pathway
3. Materials and Methods
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
Abbreviations
PBDEs | Polybrominated diphenyl ethers |
RoHs | The Restriction of the use of Certain Hazardous Substances in Electrical and Electronic Equipment |
PBB | Polybrominated biphenyls |
DFT | Density functional theory |
PM3 | Parametrized model 3 |
AM1 | Austin model 1 |
MNDO | Modified neglect of differential overlap |
TCDD | Tetrachlorodibenzodioxin |
PCDD | Polychlorinated dibenzo-p-dioxins |
PCDFs | Polychlorinated dibenzofurans |
B3LYP | Becke-Lee-Yang-Parr hybrid method |
CPCM | Conductor-like polarizable continuum model |
PES | potential energy surface scan |
TS | transition state |
IRC | intrinsic reaction coordinated |
EA | Electron affinities |
EAAda | Adiabatic electron affinities |
EAver | Vertical electron affinities |
ZPC | Zero-point corrections |
LUMO | The lowest unoccupied molecular orbital |
HOMO | The highest occupied molecular orbital |
RMSE | Root mean square error |
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No. | IUPAC Name |
---|---|
BDE-166 | 2,3,4,4′,5,6-hexa-bromodiphenyl ether |
BDE-116 | 2,3,4,5,6-penta-bromodiphenyl ether |
BDE-51 | 2,2′,4,6′-tetra-bromodiphenyl ether |
BDE-47 | 2,2′,4,4′-tetrabromodiphenyl ether |
BDE-32 | 2,4′,6-tri-bromodiphenyl ether |
BDE-30 | 2,4,6-tri-bromodiphenyl ether |
BDE-28 | 2,4,4′-tri-bromodiphenyl ether |
BDE-22 | 2,3,4′-tri-bromodiphenyl ether |
BDE-13 | 3,4′-di-bromodiphenyl ether |
BDE-8 | 2,4′-di-bromodiphenyl ether |
BDE-5 | 2,3-di-bromodiphenyl ether |
BDE-3 | 4-mono-bromodiphenyl ether |
BDE-2 | 3-mono-bromodiphenyl ether |
BDE-1 | 2-mono-bromodiphenyl ether |
Congener | Bond Length | Exptl. (Å) | Reference a | B3LYP/6-311+G(d) | Genecp | ||
---|---|---|---|---|---|---|---|
Calculated Value | Error | Calculated Value | Error | ||||
BDE-28 | Br1–C4 | 1.901 | [18] | 1.917 | 0.016 | 1.945 | 0.044 |
Br2–C8 | 1.889 | 1.907 | 0.018 | 1.933 | 0.044 | ||
Br3–C10 | 1.889 | 1.915 | 0.026 | 1.942 | 0.053 | ||
BDE-30 | Br1–C2 | 1.884 | [14] | 1.905 | 0.021 | 1.931 | 0.047 |
Br2–C6 | 1.894 | 1.912 | 0.018 | 1.931 | 0.037 | ||
Br3–C4 | 1.907 | 1.905 | -0.002 | 1.939 | 0.032 | ||
BDE-32 | Br1–C12 | 1.890 | [15] | 1.908 | 0.018 | 1.947 | 0.057 |
Br2–C8 | 1.897 | 1.908 | 0.011 | 1.934 | 0.037 | ||
Br3–C4 | 1.907 | 1.918 | 0.011 | 1.934 | 0.027 | ||
BDE-51 | Br1–C10 | 1.895 | [19] | 1.915 | 0.020 | 1.943 | 0.048 |
Br2–C12 | 1.902 | 1.906 | 0.004 | 1.932 | 0.030 | ||
Br3–C6 | 1.885 | 1.907 | 0.022 | 1.933 | 0.048 | ||
Br4–C2 | 1.879 | 1.907 | 0.028 | 1.933 | 0.054 | ||
BDE-116 | Br1–C2 | 1.866 | [17] | 1.899 | 0.033 | 1.925 | 0.059 |
Br2–C3 | 1.900 | 1.901 | 0.001 | 1.928 | 0.028 | ||
Br3–C4 | 1.880 | 1.903 | 0.023 | 1.930 | 0.050 | ||
Br4–C5 | 1.882 | 1.901 | 0.019 | 1.928 | 0.046 | ||
Br5–C6 | 1.876 | 1.899 | 0.023 | 1.925 | 0.049 | ||
BDE-166 | Br1–C4 | 1.844 | [16] | 1.917 | 0.073 | 1.945 | 0.101 |
Br2–C8 | 1.878 | 1.899 | 0.021 | 1.925 | 0.047 | ||
Br3–C9 | 1.890 | 1.900 | 0.010 | 1.927 | 0.037 | ||
Br4–C10 | 1.865 | 1.902 | 0.037 | 1.929 | 0.064 | ||
Br5–C11 | 1.883 | 1.900 | 0.017 | 1.927 | 0.044 | ||
Br6–C12 | 1.845 | 1.899 | 0.054 | 1.925 | 0.080 | ||
RMSE | 0.0268 | 0.0511 |
Congener | Bond Length | Exptl. (Å) | Reference a | B3LYP/6-311+G(d) | Genecp | ||
---|---|---|---|---|---|---|---|
Calculated Value | Error | Calculated Value | Error | ||||
BDE-28 | O–C7 | 1.380 | [18] | 1.371 | −0.009 | 1.370 | −0.010 |
O–C1 | 1.385 | 1.383 | −0.002 | 1.383 | −0.002 | ||
BDE-30 | O–C1 | 1.381 | [14] | 1.365 | −0.016 | 1.364 | −0.017 |
O–C7 | 1.394 | 1.391 | −0.003 | 1.364 | −0.030 | ||
BDE-32 | O–C7 | 1.384 | [15] | 1.369 | −0.015 | 1.368 | −0.016 |
O–C1 | 1.388 | 1.385 | −0.003 | 1.385 | −0.003 | ||
BDE-51 | O–C7 | 1.395 | [19] | 1.375 | −0.020 | 1.374 | −0.021 |
O–C1 | 1.397 | 1.371 | −0.026 | 1.370 | −0.027 | ||
BDE-116 | O–C1 | 1.371 | [17] | 1.363 | −0.008 | 1.362 | −0.009 |
O–C7 | 1.403 | 1.393 | −0.010 | 1.393 | −0.010 | ||
BDE-166 | O–C7 | 1.391 | [16] | 1.365 | −0.026 | 1.364 | −0.027 |
O–C1 | 1.414 | 1.389 | −0.025 | 1.389 | −0.025 | ||
RMSE | 0.0161 | 0.0189 |
Bond Length | BDE-22 | BDE-13 | BDE-8 | BDE-5 | BDE-3 | BDE-2 | BDE-1 |
---|---|---|---|---|---|---|---|
R1 | 1.901 | 1.082 | 1.910 | 1.902 | 1.084 | 1.082 | 1.911 |
R2 | 1.909 | 1.919 | 1.083 | 1.910 | 1.085 | 1.918 | 1.084 |
R3 | 1.083 | 1.083 | 1.084 | 1.082 | 1.085 | 1.083 | 1.084 |
R4 | 1.085 | 1.085 | 1.085 | 1.085 | 1.085 | 1.085 | 1.085 |
R5 | 1.083 | 1.084 | 1.084 | 1.083 | 1.084 | 1.083 | 1.084 |
R6 | 1.084 | 1.084 | 1.084 | 1.084 | 1.083 | 1.084 | 1.084 |
R7 | 1.083 | 1.083 | 1.083 | 1.085 | 1.083 | 1.085 | 1.085 |
R8 | 1.917 | 1.917 | 1.918 | 1.085 | 1.918 | 1.085 | 1.085 |
R9 | 1.083 | 1.083 | 1.083 | 1.085 | 1.083 | 1.085 | 1.085 |
R10 | 1.084 | 1.084 | 1.084 | 1.084 | 1.084 | 1.084 | 1.084 |
r1 | 1.399 | 1.391 | 1.393 | 1.398 | 1.394 | 1.389 | 1.392 |
r2 | 1.394 | 1.391 | 1.392 | 1.395 | 1.394 | 1.392 | 1.393 |
r3 | 1.390 | 1.395 | 1.394 | 1.390 | 1.395 | 1.394 | 1.394 |
r4 | 1.390 | 1.391 | 1.391 | 1.390 | 1.393 | 1.393 | 1.391 |
r5 | 1.394 | 1.394 | 1.397 | 1.394 | 1.395 | 1.395 | 1.397 |
r6 | 1.405 | 1.396 | 1.398 | 1.407 | 1.392 | 1.396 | 1.400 |
r7 | 1.371 | 1.379 | 1.374 | 1.368 | 1.386 | 1.376 | 1.371 |
r8 | 1.384 | 1.382 | 1.381 | 1.389 | 1.377 | 1.386 | 1.386 |
r9 | 1.392 | 1.392 | 1.393 | 1.391 | 1.395 | 1.392 | 1.392 |
r10 | 1.393 | 1.393 | 1.392 | 1.394 | 1.391 | 1.394 | 1.394 |
r11 | 1.392 | 1.392 | 1.392 | 1.394 | 1.392 | 1.394 | 1.394 |
r12 | 1.393 | 1.392 | 1.392 | 1.395 | 1.391 | 1.395 | 1.395 |
r13 | 1.393 | 1.393 | 1.393 | 1.393 | 1.394 | 1.393 | 1.393 |
r14 | 1.394 | 1.395 | 1.394 | 1.394 | 1.395 | 1.395 | 1.394 |
θ1 | 119.0 | 118.4 | 120.4 | 119.1 | 119.5 | 118.8 | 120.5 |
θ2 | 120.7 | 122.0 | 120.0 | 120.8 | 120.4 | 121.8 | 120.0 |
θ3 | 119.6 | 118.4 | 119.8 | 119.4 | 119.6 | 118.3 | 119.7 |
θ4 | 120.6 | 121.0 | 120.2 | 120.7 | 120.6 | 121.4 | 120.3 |
θ5 | 119.8 | 119.3 | 120.3 | 119.9 | 119.2 | 119.0 | 120.3 |
θ6 | 120.3 | 120.9 | 119.3 | 120.1 | 120.8 | 120.7 | 119.1 |
θ7 | 119.8 | 119.9 | 119.9 | 119.3 | 120.1 | 119.4 | 119.4 |
θ8 | 120.6 | 120.5 | 120.5 | 121.1 | 120.2 | 120.8 | 120.9 |
θ9 | 119.6 | 119.7 | 119.7 | 119.1 | 119.7 | 119.2 | 119.2 |
θ10 | 119.6 | 119.6 | 119.7 | 120.5 | 119.7 | 120.5 | 120.6 |
θ11 | 120.9 | 120.9 | 120.9 | 119.7 | 120.8 | 119.6 | 119.6 |
θ12 | 119.4 | 119.4 | 119.4 | 120.3 | 119.5 | 120.4 | 120.4 |
θ13 | 120.7 | 121.0 | 120.7 | 120.7 | 120.8 | 120.8 | 120.8 |
Bond Length | BDE-22 | BDE-13 | BDE-8 | BDE-5 | BDE-3 | BDE-2 | BDE-1 |
---|---|---|---|---|---|---|---|
R1 | 1.958 | 1.088 | 2.793 | 1.957 | 1.085 | 1.087 | 2.806 |
R2 | 2.635 | 2.754 | 1.086 | 2.668 | 1.086 | 2.786 | 1.086 |
R3 | 1.087 | 1.087 | 1.088 | 1.087 | 1.085 | 1.087 | 1.088 |
R4 | 1.088 | 1.089 | 1.087 | 1.088 | 1.086 | 1.089 | 1.087 |
R5 | 1.085 | 1.085 | 1.087 | 1.085 | 1.083 | 1.085 | 1.087 |
R6 | 1.083 | 1.083 | 1.085 | 1.083 | 1.088 | 1.085 | 1.085 |
R7 | 1.084 | 1.084 | 1.084 | 1.083 | 1.088 | 1.086 | 1.087 |
R8 | 1.928 | 1.928 | 1.933 | 1.085 | 2.780 | 1.085 | 1.086 |
R9 | 1.084 | 1.084 | 1.083 | 1.086 | 1.088 | 1.086 | 1.086 |
R10 | 1.084 | 1.085 | 1.081 | 1.085 | 1.088 | 1.083 | 1.081 |
r1 | 1.368 | 1.387 | 1.388 | 1.368 | 1.390 | 1.386 | 1.387 |
r2 | 1.389 | 1.388 | 1.399 | 1.388 | 1.397 | 1.387 | 1.399 |
r3 | 1.397 | 1.399 | 1.397 | 1.397 | 1.393 | 1.399 | 1.397 |
r4 | 1.396 | 1.398 | 1.393 | 1.396 | 1.395 | 1.398 | 1.393 |
r5 | 1.392 | 1.391 | 1.401 | 1.393 | 1.399 | 1.392 | 1.401 |
r6 | 1.400 | 1.395 | 1.382 | 1.400 | 1.401 | 1.396 | 1.383 |
r7 | 1.400 | 1.411 | 1.403 | 1.397 | 1.365 | 1.408 | 1.400 |
r8 | 1.364 | 1.361 | 1.365 | 1.368 | 1.409 | 1.365 | 1.369 |
r9 | 1.399 | 1.401 | 1.397 | 1.399 | 1.392 | 1.398 | 1.396 |
r10 | 1.390 | 1.390 | 1.395 | 1.390 | 1.402 | 1.395 | 1.394 |
r11 | 1.392 | 1.392 | 1.389 | 1.397 | 1.386 | 1.394 | 1.394 |
r12 | 1.389 | 1.389 | 1.391 | 1.393 | 1.386 | 1.397 | 1.396 |
r13 | 1.394 | 1.394 | 1.390 | 1.394 | 1.402 | 1.390 | 1.391 |
r14 | 1.397 | 1.399 | 1.401 | 1.397 | 1.392 | 1.401 | 1.401 |
θ1 | 120.4 | 118.5 | 119.6 | 120.5 | 120.1 | 118.5 | 119.7 |
θ2 | 120.4 | 121.2 | 120.5 | 120.5 | 120.6 | 121.4 | 120.5 |
θ3 | 119.9 | 119.6 | 119.7 | 119.7 | 119.0 | 119.5 | 119.7 |
θ4 | 119.9 | 120.3 | 119.8 | 119.9 | 121.1 | 120.3 | 119.8 |
θ5 | 119.6 | 118.7 | 119.7 | 119.7 | 119.5 | 118.8 | 119.8 |
θ6 | 119.8 | 121.8 | 120.7 | 119.6 | 119.7 | 121.6 | 120.5 |
θ7 | 120.5 | 120.6 | 119.6 | 120.0 | 119.0 | 119.4 | 119.1 |
θ8 | 119.7 | 119.5 | 119.7 | 119.9 | 121.3 | 119.8 | 119.9 |
θ9 | 119.9 | 119.9 | 120.7 | 119.4 | 119.0 | 120.1 | 120.3 |
θ10 | 119.8 | 119.9 | 118.9 | 121.1 | 119.9 | 120.6 | 120.3 |
θ11 | 120.9 | 120.8 | 121.0 | 119.0 | 120.7 | 119.0 | 119.0 |
θ12 | 119.3 | 119.3 | 120.0 | 120.6 | 119.9 | 121.2 | 121.4 |
θ13 | 119.6 | 119.7 | 123.3 | 119.8 | 119.4 | 119.9 | 123.1 |
Congeners | Ortho-Position | Meta-Position | Para-Position |
---|---|---|---|
BDE-22 | 178.5 | −165.7 | 179.9 |
BDE-13 | - | −162.5 | 179.9 |
BDE-8 | −174.1 | - | 179.5 |
BDE-5 | 179.4 | −175.8 | - |
BDE-3 | - | - | −173.2 |
BDE-2 | - | 166.5 | - |
BDE-1 | −177.7 | - | - |
EA | BDE-22 | BDE-13 | BDE-8 | BDE-5 | BDE-3 | BDE-2 | BDE-1 | |
---|---|---|---|---|---|---|---|---|
EAAda | au | 0.0392 | 0.0277 | 0.0306 | 0.0350 | 0.0230 | 0.0238 | 0.0250 |
eV | 1.066 | 0.753 | 0.832 | 0.951 | 0.626 | 0.647 | 0.681 | |
EAver | au | 0.0082 | 0.0046 | 0.0029 | 0.0017 | −0.0053 | −0.0061 | −0.0080 |
eV | 0.223 | 0.124 | 0.079 | 0.046 | −0.145 | −0.167 | −0.218 |
Orbit | BDE-47 | BDE-22 | BDE-13 | BDE-8 | BDE-5 | BDE-3 | BDE-2 | BDE-1 |
---|---|---|---|---|---|---|---|---|
EHOMO | −0.24561 | −0.24321 | −0.24051 | −0.23786 | −0.2419 | −0.23279 | −0.23812 | −0.23537 |
ELUMO | −0.05789 | −0.05047 | −0.04592 | −0.0443 | −0.04342 | −0.03813 | −0.03744 | −0.03597 |
© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/).
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Li, L.; Hu, J.; Shi, X.; Ruan, W.; Luo, J.; Wei, X. Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers. Int. J. Mol. Sci. 2016, 17, 927. https://doi.org/10.3390/ijms17060927
Li L, Hu J, Shi X, Ruan W, Luo J, Wei X. Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers. International Journal of Molecular Sciences. 2016; 17(6):927. https://doi.org/10.3390/ijms17060927
Chicago/Turabian StyleLi, Lingyun, Jiwei Hu, Xuedan Shi, Wenqian Ruan, Jin Luo, and Xionghui Wei. 2016. "Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers" International Journal of Molecular Sciences 17, no. 6: 927. https://doi.org/10.3390/ijms17060927