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

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

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)1378-1387
Number of pages10
JournalInternational Journal of Quantum Chemistry
Volume90
Issue number4-5
DOIs
Publication statusPublished - 15 Nov 2002

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Keywords

  • 2-methyl-4-nitroaniline
  • Charge transfer
  • Electronic excitation energies
  • First hyperpolarizability
  • Molecular crystal

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