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On the relationship between bond-length alternation and many-electron self-interaction error
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10.1063/1.4752431
/content/aip/journal/jcp/137/12/10.1063/1.4752431
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/12/10.1063/1.4752431
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

BLA at the central carbon atoms of polyenes H–(HC=CH) n –H as calculated with CCSD(T), HF, PBE, and PBEh. HF and DFT calculations employed a cc-pVTZ basis. CCSD(T) geometries employed a 6-31G(d) basis set.

Image of FIG. 2.
FIG. 2.

Deviation of total energy from that of the neutral molecule (top), deviation of total energy from straight line (ΔE) (top inset), and HOMO eigenvalue (bottom) as a function of the fractional deviation of the number of electrons from that of the neutral molecule δ, calculated for C16H18 using HF, PBEh, and PBE and a jun-cc-pVTZ43 basis set.

Image of FIG. 3.
FIG. 3.

Central BLA of polyenes H–(HC=CH) n –H from the standard (open symbols) and IP-tuned (filled symbols) long-range corrected hybrids ωPBE (squares), ωPBEh (triangle up), ωB97 (circles), and ωB97X (triangle right).

Image of FIG. 4.
FIG. 4.

Deviation of total energy from straight line (ΔE) as a function of the fractional deviation of the number of electrons from that of the neutral molecule δ, calculated for H–(HC=CH) n –H with n = 8 (top) and n = 16 (bottom) using the standard (ω = 0.4 bohr−1) and IP-optimized (ω = 0.186 bohr−1 for n = 8, ω = 0.136 bohr−1 for n = 16) ωPBE.

Image of FIG. 5.
FIG. 5.

Central BLA of C16H18 from ωPBE (red dashed line) and the global hybrid PBEα (blue solid line) as a function of ω and α, respectively. The dotted lines indicate the BLAs obtained from PBE, HF, and the CCSD(T) benchmark. The red and blue dots mark the standard values for ω and α in ωPBE and PBEh, respectively.

Image of FIG. 6.
FIG. 6.

IP-tuned range-separation parameter ω for H–(HC=CH) n –H for ωPBE (squares) and ωPBEh (triangles) as a function of n.

Image of FIG. 7.
FIG. 7.

Deviation of total energy from straight line (ΔE) (top) and HOMO eigenvalue (bottom) as a function of the fractional number of electrons (neutral molecule for N = 58) calculated for C8H10 using PBEh (dots) as well as the standard (squares) and IP-optimized (triangles) ωPBE.

Image of FIG. 8.
FIG. 8.

(Top) Central BLA of polyenes H–(HC=CH) n –H from CCSD(T) (diamonds) and the “BLA-tuned” ωPBE (squares) and PBEα (triangles) as a function of n. (Bottom) Corresponding HOMO MSIE (see text) as a function of n.

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/content/aip/journal/jcp/137/12/10.1063/1.4752431
2012-09-24
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: On the relationship between bond-length alternation and many-electron self-interaction error
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/12/10.1063/1.4752431
10.1063/1.4752431
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