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.
N1 - Funding Information:
B.C. and D.J. thank the Belgian National Fund for Scientific Research for their Senior Research Associate and Post-Doctoral Researcher positions, respectively. D.M.B. and F.L.G. are grateful to the Natural Sciences and Engineering Research Council of Canada for financial support and to Queen’s University (Canada) for the use of computer facilities. F.L.G. thanks the Japan Society for the Promotion of Science (JSPS) for his stay in Japan and financial support from the Grant-in-Aid for Scientific Research JSPS. Some of the calculations were performed on IBM workstations at Hiroshima University.
Copyright:
Copyright 2004 Elsevier Science B.V., Amsterdam. All rights reserved.
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.
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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 -