Saturation of the second hyperpolarizability for polyacetylenes

Lu Daqi; Bryan Marten; Murco Ringnalda; Richard A. Friesner; William A. Goddard

doi:10.1016/0009-2614(96)00458-7

Saturation of the second hyperpolarizability for polyacetylenes

Lu Daqi
, Bryan Marten
, Murco Ringnalda
, Richard A. Friesner
, William A. Goddard

Research output: Contribution to journal › Article › peer-review

Abstract

Polyacetylene (PA) polymers -(-CH=CH-)_N-lead to large second hyperpolarizabilities (γ) that increase with N. For small N the increase is quite rapid, eventually saturating (becoming linear in N) for N ≥ N^γ_sat. Both experimental and theoretical attempts have been made to estimate N^γ_sat. In 1994 this led to two Science papers, one obtaining N^γ_sat = 20 (semiempirical theory) and the other obtaining N^γ_sat = 125 (experiment, but on a substituted disordered form of PA!). We report here ab initio calculations up through N = 49 (C₉₈H₁₀₀) and show that N^γ_sat = 45 ± 5. The much larger experimental value, N^γ_sat = 125, is explained in terms of the structural defects and disorder introduced by the synthetic method.

Original language	English
Pages (from-to)	224-228
Number of pages	5
Journal	Chemical Physics Letters
Volume	257
Issue number	3-4
DOIs	https://doi.org/10.1016/0009-2614(96)00458-7
Publication status	Published - 26 Jul 1996
Externally published	Yes

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title = "Saturation of the second hyperpolarizability for polyacetylenes",

abstract = "Polyacetylene (PA) polymers -(-CH=CH-)N-lead to large second hyperpolarizabilities (γ) that increase with N. For small N the increase is quite rapid, eventually saturating (becoming linear in N) for N ≥ Nγsat. Both experimental and theoretical attempts have been made to estimate Nγsat. In 1994 this led to two Science papers, one obtaining Nγsat = 20 (semiempirical theory) and the other obtaining Nγsat = 125 (experiment, but on a substituted disordered form of PA!). We report here ab initio calculations up through N = 49 (C98H100) and show that Nγsat = 45 ± 5. The much larger experimental value, Nγsat = 125, is explained in terms of the structural defects and disorder introduced by the synthetic method.",

author = "Lu Daqi and Bryan Marten and Murco Ringnalda and Friesner, \{Richard A.\} and Goddard, \{William A.\}",

year = "1996",

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doi = "10.1016/0009-2614(96)00458-7",

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pages = "224--228",

journal = "Chemical Physics Letters",

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TY - JOUR

T1 - Saturation of the second hyperpolarizability for polyacetylenes

AU - Daqi, Lu

AU - Marten, Bryan

AU - Ringnalda, Murco

AU - Friesner, Richard A.

AU - Goddard, William A.

PY - 1996/7/26

Y1 - 1996/7/26

N2 - Polyacetylene (PA) polymers -(-CH=CH-)N-lead to large second hyperpolarizabilities (γ) that increase with N. For small N the increase is quite rapid, eventually saturating (becoming linear in N) for N ≥ Nγsat. Both experimental and theoretical attempts have been made to estimate Nγsat. In 1994 this led to two Science papers, one obtaining Nγsat = 20 (semiempirical theory) and the other obtaining Nγsat = 125 (experiment, but on a substituted disordered form of PA!). We report here ab initio calculations up through N = 49 (C98H100) and show that Nγsat = 45 ± 5. The much larger experimental value, Nγsat = 125, is explained in terms of the structural defects and disorder introduced by the synthetic method.

AB - Polyacetylene (PA) polymers -(-CH=CH-)N-lead to large second hyperpolarizabilities (γ) that increase with N. For small N the increase is quite rapid, eventually saturating (becoming linear in N) for N ≥ Nγsat. Both experimental and theoretical attempts have been made to estimate Nγsat. In 1994 this led to two Science papers, one obtaining Nγsat = 20 (semiempirical theory) and the other obtaining Nγsat = 125 (experiment, but on a substituted disordered form of PA!). We report here ab initio calculations up through N = 49 (C98H100) and show that Nγsat = 45 ± 5. The much larger experimental value, Nγsat = 125, is explained in terms of the structural defects and disorder introduced by the synthetic method.

UR - https://www.scopus.com/pages/publications/0030602756

U2 - 10.1016/0009-2614(96)00458-7

DO - 10.1016/0009-2614(96)00458-7

M3 - Article

AN - SCOPUS:0030602756

SN - 0009-2614

VL - 257

SP - 224

EP - 228

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 3-4

ER -

Saturation of the second hyperpolarizability for polyacetylenes

Abstract

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