Abstract
Effects of pseudo linear-dependence and long-range interactions in calculating (hyper)polarizabilities of several stereoregular polymers are addressed. Long-range Coulomb interactions in the TDHF equations can be accurately determined using a multipole expansion. Although these terms are small they ensure fast convergence with the size of the medium-range region and are often compulsory for SCF convergence. We find that (hyper)polarizabilities can be significantly underestimated by eliminating columns of the transformation matrix associated with small eigenvalues in the procedure to remove pseudo linear-dependencies. Finally, exchange interactions converge rapidly with the size of the short-range region.
| Original language | English |
|---|---|
| Pages (from-to) | 539-549 |
| Number of pages | 11 |
| Journal | Chemical Physics Letters |
| Volume | 373 |
| Issue number | 5-6 |
| DOIs | |
| Publication status | Published - May 28 2003 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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Pseudo linear-dependence and long-range interaction effects on the polarizability and hyperpolarizabilities of stereoregular polymers. / Champagne, Benôt; Jacquemin, Denis; Gu, Feng Long; Aoki, Yuriko; Kirtman, Bernard; Bishop, David M.
In: Chemical Physics Letters, Vol. 373, No. 5-6, 28.05.2003, p. 539-549.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Pseudo linear-dependence and long-range interaction effects on the polarizability and hyperpolarizabilities of stereoregular polymers
AU - Champagne, Benôt
AU - Jacquemin, Denis
AU - Gu, Feng Long
AU - Aoki, Yuriko
AU - Kirtman, Bernard
AU - Bishop, David M.
PY - 2003/5/28
Y1 - 2003/5/28
N2 - Effects of pseudo linear-dependence and long-range interactions in calculating (hyper)polarizabilities of several stereoregular polymers are addressed. Long-range Coulomb interactions in the TDHF equations can be accurately determined using a multipole expansion. Although these terms are small they ensure fast convergence with the size of the medium-range region and are often compulsory for SCF convergence. We find that (hyper)polarizabilities can be significantly underestimated by eliminating columns of the transformation matrix associated with small eigenvalues in the procedure to remove pseudo linear-dependencies. Finally, exchange interactions converge rapidly with the size of the short-range region.
AB - Effects of pseudo linear-dependence and long-range interactions in calculating (hyper)polarizabilities of several stereoregular polymers are addressed. Long-range Coulomb interactions in the TDHF equations can be accurately determined using a multipole expansion. Although these terms are small they ensure fast convergence with the size of the medium-range region and are often compulsory for SCF convergence. We find that (hyper)polarizabilities can be significantly underestimated by eliminating columns of the transformation matrix associated with small eigenvalues in the procedure to remove pseudo linear-dependencies. Finally, exchange interactions converge rapidly with the size of the short-range region.
UR - http://www.scopus.com/inward/record.url?scp=0037846139&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0037846139&partnerID=8YFLogxK
U2 - 10.1016/S0009-2614(03)00631-6
DO - 10.1016/S0009-2614(03)00631-6
M3 - Article
AN - SCOPUS:0037846139
VL - 373
SP - 539
EP - 549
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 5-6
ER -