Electronic excitations and first hyperpolarizability of 2-methyl-4-nitroaniline clusters

Maxime Guillaume, Edith Botek, Benoit Champagne, Frédéric Castet, L. Ducasse

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

The crystal packing effects upon the static and dynamic first hyperpolarizability of 2-methyl-4-nitroaniline (MNA) clusters have been addressed at the TDHF/AM1 level. Due to electrostatic interactions, in 1-D arrays of MNA unit cells extending along the a crystallographic axis, the effective hyperpolarizability strongly increases whereas stacking unit cells along the b or c axes leads to a reduction of these quantities. These effects are magnified in the case of frequency-dependent quantifies. The first hyperpolarizability variations can mostly be related to bathochromatic and hypsochromatic shifts as well as to changes in transition dipole moments of the low-energy excited states that dominate the UV/visible absorption spectra. From calculations performed at the CIS/INDO/S level of approximation, these dominant excited states present an important intramolecular charge transfer character and bathochromatic (hypsochromatic) shifts are associated with increase (decrease) of the transition dipole moments. In addition, a large number of intermolecular charge-transfer excited states have been detected. In the small MNA aggregates as well as in clusters extending only along the b or c crystallographic axes, these excited states possess small transition dipole moments. On the other hand, when stacking MNA unit cells along the a axis the electrostatic interactions induce a decrease of the excitation energies and an increase of the transition dipole moments of these intermolecular charge transfer states. As a consequence, they account for a nonnegligible contribution to the first hyperpolarizability.

langue originaleAnglais
Pages (de - à)1378-1387
Nombre de pages10
journalInternational Journal of Quantum Chemistry
Volume90
Numéro de publication4-5
Les DOIs
étatPublié - 15 nov. 2002

Empreinte digitale

Dipole moment
Excited states
Electron transitions
Charge transfer
dipole moments
Coulomb interactions
electronics
excitation
charge transfer
cells
Excitation energy
electrostatics
Commonwealth of Independent States
shift
Absorption spectra
visible spectrum
Crystals
4-nitroaniline
interactions
absorption spectra

Citer ceci

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title = "Electronic excitations and first hyperpolarizability of 2-methyl-4-nitroaniline clusters",
abstract = "The crystal packing effects upon the static and dynamic first hyperpolarizability of 2-methyl-4-nitroaniline (MNA) clusters have been addressed at the TDHF/AM1 level. Due to electrostatic interactions, in 1-D arrays of MNA unit cells extending along the a crystallographic axis, the effective hyperpolarizability strongly increases whereas stacking unit cells along the b or c axes leads to a reduction of these quantities. These effects are magnified in the case of frequency-dependent quantifies. The first hyperpolarizability variations can mostly be related to bathochromatic and hypsochromatic shifts as well as to changes in transition dipole moments of the low-energy excited states that dominate the UV/visible absorption spectra. From calculations performed at the CIS/INDO/S level of approximation, these dominant excited states present an important intramolecular charge transfer character and bathochromatic (hypsochromatic) shifts are associated with increase (decrease) of the transition dipole moments. In addition, a large number of intermolecular charge-transfer excited states have been detected. In the small MNA aggregates as well as in clusters extending only along the b or c crystallographic axes, these excited states possess small transition dipole moments. On the other hand, when stacking MNA unit cells along the a axis the electrostatic interactions induce a decrease of the excitation energies and an increase of the transition dipole moments of these intermolecular charge transfer states. As a consequence, they account for a nonnegligible contribution to the first hyperpolarizability.",
keywords = "2-methyl-4-nitroaniline, Charge transfer, Electronic excitation energies, First hyperpolarizability, Molecular crystal",
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Electronic excitations and first hyperpolarizability of 2-methyl-4-nitroaniline clusters. / Guillaume, Maxime; Botek, Edith; Champagne, Benoit; Castet, Frédéric; Ducasse, L.

Dans: International Journal of Quantum Chemistry, Vol 90, Numéro 4-5, 15.11.2002, p. 1378-1387.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Electronic excitations and first hyperpolarizability of 2-methyl-4-nitroaniline clusters

AU - Guillaume, Maxime

AU - Botek, Edith

AU - Champagne, Benoit

AU - Castet, Frédéric

AU - Ducasse, L.

PY - 2002/11/15

Y1 - 2002/11/15

N2 - The crystal packing effects upon the static and dynamic first hyperpolarizability of 2-methyl-4-nitroaniline (MNA) clusters have been addressed at the TDHF/AM1 level. Due to electrostatic interactions, in 1-D arrays of MNA unit cells extending along the a crystallographic axis, the effective hyperpolarizability strongly increases whereas stacking unit cells along the b or c axes leads to a reduction of these quantities. These effects are magnified in the case of frequency-dependent quantifies. The first hyperpolarizability variations can mostly be related to bathochromatic and hypsochromatic shifts as well as to changes in transition dipole moments of the low-energy excited states that dominate the UV/visible absorption spectra. From calculations performed at the CIS/INDO/S level of approximation, these dominant excited states present an important intramolecular charge transfer character and bathochromatic (hypsochromatic) shifts are associated with increase (decrease) of the transition dipole moments. In addition, a large number of intermolecular charge-transfer excited states have been detected. In the small MNA aggregates as well as in clusters extending only along the b or c crystallographic axes, these excited states possess small transition dipole moments. On the other hand, when stacking MNA unit cells along the a axis the electrostatic interactions induce a decrease of the excitation energies and an increase of the transition dipole moments of these intermolecular charge transfer states. As a consequence, they account for a nonnegligible contribution to the first hyperpolarizability.

AB - The crystal packing effects upon the static and dynamic first hyperpolarizability of 2-methyl-4-nitroaniline (MNA) clusters have been addressed at the TDHF/AM1 level. Due to electrostatic interactions, in 1-D arrays of MNA unit cells extending along the a crystallographic axis, the effective hyperpolarizability strongly increases whereas stacking unit cells along the b or c axes leads to a reduction of these quantities. These effects are magnified in the case of frequency-dependent quantifies. The first hyperpolarizability variations can mostly be related to bathochromatic and hypsochromatic shifts as well as to changes in transition dipole moments of the low-energy excited states that dominate the UV/visible absorption spectra. From calculations performed at the CIS/INDO/S level of approximation, these dominant excited states present an important intramolecular charge transfer character and bathochromatic (hypsochromatic) shifts are associated with increase (decrease) of the transition dipole moments. In addition, a large number of intermolecular charge-transfer excited states have been detected. In the small MNA aggregates as well as in clusters extending only along the b or c crystallographic axes, these excited states possess small transition dipole moments. On the other hand, when stacking MNA unit cells along the a axis the electrostatic interactions induce a decrease of the excitation energies and an increase of the transition dipole moments of these intermolecular charge transfer states. As a consequence, they account for a nonnegligible contribution to the first hyperpolarizability.

KW - 2-methyl-4-nitroaniline

KW - Charge transfer

KW - Electronic excitation energies

KW - First hyperpolarizability

KW - Molecular crystal

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