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Chiral and achiral contributions to sum-frequency generation from optically active solutions of binaphthol

2003

Article

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The nonlinear sum- and difference-frequency generation spectroscopies can be probes of molecular chirality in optically active systems. We present a tensorial analysis of the chirality-specific electric-dipolar sum-frequency-generation susceptibility and the achiral electric-quadrupolar and magnetic-dipolar nonlinearities at second order in isotropic media. The chiral and achiral contributions to the sum-frequency signal from the bulk of optically active solutions of 1,1'-bi-2-naphthol (2,2'-dehydroxy-1,1'-binaphthyl) can be distinguished, and the former dominates. Ab initio computations reveal the dramatic resonance enhancement that the isotropic component of the electric-dipolar three-wave mixing hyperpolarizability experiences. Away from resonance its magnitude rapidly decreases, as-unlike the vector component-it is zero in the static limit. The dispersion of the first hyperpolarizability is computed by a configuration interaction singles sum-over-states approach with explicit regard to the Franck-Condon active vibrational substructure for all resonant electronic states.

Author(s): Fischer, Peer and Wise, FW and Albrecht, AC
Journal: JOURNAL OF PHYSICAL CHEMISTRY A
Volume: 107
Number (issue): 40
Pages: 8232-8238
Year: 2003

Department(s): Micro, Nano, and Molecular Systems
Bibtex Type: Article (article)

DOI: 10.1021/jp027861+

BibTex

@article{ISI:000185757100028,
  title = {Chiral and achiral contributions to sum-frequency generation from optically active solutions of binaphthol},
  author = {Fischer, Peer and Wise, FW and Albrecht, AC},
  journal = {JOURNAL OF PHYSICAL CHEMISTRY A},
  volume = {107},
  number = {40},
  pages = {8232-8238},
  year = {2003}
}