Intramolecular charge transfer and first-order hyperpolarizability of planar and twisted sesquifulvalenes

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

MP2/6-31+G(d) calculations are used to compare the static electronic first hyperpolarizability (β) of planar and twisted sesquifulvalenes. The longitudinal component of β which is dominant in both structures is more than five times larger in the twisted form where it points in the opposite direction from the dipole moment. This larger β value can be related to the much larger second-order charge derivatives with respect to an electric field. Moreover, using the SOS scheme, the β of the twisted form is shown to originate from a single low-lying excited state characterized by the transfer of one electron from the five-membered to the seven-membered ring. The enhancement due to twisting supports the phenomenon of sudden polarization in polar hydrocarbons and leads to β values that are of the same order of magnitude as in push-pull conjugated polyenes of similar size. Our analysis suggests that substituting the inter-ring carbon atoms by heteroatoms will result in substantial changes in β.

langue originaleAnglais
Pages (de - à)5566-5571
Nombre de pages6
journalPhysical Chemistry Chemical Physics
Volume4
Numéro de publication22
Les DOIs
étatPublié - 28 nov. 2002

Empreinte digitale

Polyenes
Dipole moment
Hydrocarbons
Excited states
Charge transfer
Carbon
charge transfer
Electric fields
Polarization
Derivatives
Atoms
Electrons
rings
twisting
dipole moments
hydrocarbons
electric fields
augmentation
carbon
polarization

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abstract = "MP2/6-31+G(d) calculations are used to compare the static electronic first hyperpolarizability (β) of planar and twisted sesquifulvalenes. The longitudinal component of β which is dominant in both structures is more than five times larger in the twisted form where it points in the opposite direction from the dipole moment. This larger β value can be related to the much larger second-order charge derivatives with respect to an electric field. Moreover, using the SOS scheme, the β of the twisted form is shown to originate from a single low-lying excited state characterized by the transfer of one electron from the five-membered to the seven-membered ring. The enhancement due to twisting supports the phenomenon of sudden polarization in polar hydrocarbons and leads to β values that are of the same order of magnitude as in push-pull conjugated polyenes of similar size. Our analysis suggests that substituting the inter-ring carbon atoms by heteroatoms will result in substantial changes in β.",
author = "Mingli Yang and Denis Jacquemin and Beno{\^i}t Champagne",
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Intramolecular charge transfer and first-order hyperpolarizability of planar and twisted sesquifulvalenes. / Yang, Mingli; Jacquemin, Denis; Champagne, Benoît.

Dans: Physical Chemistry Chemical Physics, Vol 4, Numéro 22, 28.11.2002, p. 5566-5571.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Intramolecular charge transfer and first-order hyperpolarizability of planar and twisted sesquifulvalenes

AU - Yang, Mingli

AU - Jacquemin, Denis

AU - Champagne, Benoît

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AB - MP2/6-31+G(d) calculations are used to compare the static electronic first hyperpolarizability (β) of planar and twisted sesquifulvalenes. The longitudinal component of β which is dominant in both structures is more than five times larger in the twisted form where it points in the opposite direction from the dipole moment. This larger β value can be related to the much larger second-order charge derivatives with respect to an electric field. Moreover, using the SOS scheme, the β of the twisted form is shown to originate from a single low-lying excited state characterized by the transfer of one electron from the five-membered to the seven-membered ring. The enhancement due to twisting supports the phenomenon of sudden polarization in polar hydrocarbons and leads to β values that are of the same order of magnitude as in push-pull conjugated polyenes of similar size. Our analysis suggests that substituting the inter-ring carbon atoms by heteroatoms will result in substantial changes in β.

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