Electronic and vibrational first hyperpolarizabilities of polymethineimine oligomers

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Abstract

The longitudinal static electronic and vibrational first hyperpolarizabilities of nonplanar trans-cisoid polymethineimine oligomers of increasing size have been evaluated at the Hartree-Fock 6-31G level and with the double harmonic approximation. It turns out that the vibrational static first hyperpolarizability per unit cell is very large and still increases linearly with chain length for oligomers containing fifteen unit cells, whereas its electronic counterpart tends to saturate. The vibrational component also contributes substantially to the dc-Pockels and Optical Rectification processes but not to the second harmonic generation phenomenon. The analysis of the vibrational first hyperpolarizability shows that the vibrational normal modes contributing the most have frequencies larger than 1000 cm-1 and involve variations of the bond length alternation along the chain backbone. The effects of electron correlation on the static electronic first hyperpolarizability are also addressed. (C) 2000 Elsevier Science B.V.

Original languageEnglish
Pages (from-to)65-71
Number of pages7
JournalJournal of Molecular Structure: THEOCHEM
Volume529
DOIs
Publication statusPublished - 8 Sep 2000

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oligomers
Oligomers
Optical Phenomena
Electron correlations
Bond length
Harmonic generation
Chain length
electronics
alternations
rectification
Electrons
cells
harmonic generations
harmonics
approximation
electrons

Keywords

  • Hartree-Fock evaluations
  • Hyperpolarizabilities
  • Polymethineimine oligomers

Cite this

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title = "Electronic and vibrational first hyperpolarizabilities of polymethineimine oligomers",
abstract = "The longitudinal static electronic and vibrational first hyperpolarizabilities of nonplanar trans-cisoid polymethineimine oligomers of increasing size have been evaluated at the Hartree-Fock 6-31G level and with the double harmonic approximation. It turns out that the vibrational static first hyperpolarizability per unit cell is very large and still increases linearly with chain length for oligomers containing fifteen unit cells, whereas its electronic counterpart tends to saturate. The vibrational component also contributes substantially to the dc-Pockels and Optical Rectification processes but not to the second harmonic generation phenomenon. The analysis of the vibrational first hyperpolarizability shows that the vibrational normal modes contributing the most have frequencies larger than 1000 cm-1 and involve variations of the bond length alternation along the chain backbone. The effects of electron correlation on the static electronic first hyperpolarizability are also addressed. (C) 2000 Elsevier Science B.V.",
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author = "Perp{\`e}te, {E. A.} and B. Champagne and D. Jacquemin",
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journal = "Journal of Molecular Structure: THEOCHEM",
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TY - JOUR

T1 - Electronic and vibrational first hyperpolarizabilities of polymethineimine oligomers

AU - Perpète, E. A.

AU - Champagne, B.

AU - Jacquemin, D.

PY - 2000/9/8

Y1 - 2000/9/8

N2 - The longitudinal static electronic and vibrational first hyperpolarizabilities of nonplanar trans-cisoid polymethineimine oligomers of increasing size have been evaluated at the Hartree-Fock 6-31G level and with the double harmonic approximation. It turns out that the vibrational static first hyperpolarizability per unit cell is very large and still increases linearly with chain length for oligomers containing fifteen unit cells, whereas its electronic counterpart tends to saturate. The vibrational component also contributes substantially to the dc-Pockels and Optical Rectification processes but not to the second harmonic generation phenomenon. The analysis of the vibrational first hyperpolarizability shows that the vibrational normal modes contributing the most have frequencies larger than 1000 cm-1 and involve variations of the bond length alternation along the chain backbone. The effects of electron correlation on the static electronic first hyperpolarizability are also addressed. (C) 2000 Elsevier Science B.V.

AB - The longitudinal static electronic and vibrational first hyperpolarizabilities of nonplanar trans-cisoid polymethineimine oligomers of increasing size have been evaluated at the Hartree-Fock 6-31G level and with the double harmonic approximation. It turns out that the vibrational static first hyperpolarizability per unit cell is very large and still increases linearly with chain length for oligomers containing fifteen unit cells, whereas its electronic counterpart tends to saturate. The vibrational component also contributes substantially to the dc-Pockels and Optical Rectification processes but not to the second harmonic generation phenomenon. The analysis of the vibrational first hyperpolarizability shows that the vibrational normal modes contributing the most have frequencies larger than 1000 cm-1 and involve variations of the bond length alternation along the chain backbone. The effects of electron correlation on the static electronic first hyperpolarizability are also addressed. (C) 2000 Elsevier Science B.V.

KW - Hartree-Fock evaluations

KW - Hyperpolarizabilities

KW - Polymethineimine oligomers

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