Application of time-dependent Raman theory to Raman excitation profiles of hexamethylbenzene-tetracyanoethylene electron donor-acceptor complex

Journal Article · Thu Apr 27 04:00:00 EDT 1995 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100017a014· OSTI ID:50501

Britt, B M; McHale, J L ^[1]; Friedrich, D M ^[2]

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1. Univ. of Idaho, Moscow, ID (United States)
2. Pacific Northwest Lab., Richland, WA (United States)

Raman excitation and absorption profiles were obtained for the 1:1 electron donor-acceptor complex of hexamethylbenzene with tetracyanoethylene in dichloromethane solution. The absorption and Raman profiles were analyzed using the time-dependent theory of Heller to obtain the displacements and non-Condon factors for the four strongest Raman modes, the electronic excitation energy, the transition dipole, and solvent line-broadening parameters. The results are compared to the data reported by Myers et al. for the same complex in carbon tetrachloride solution. Attempts to account for solvent effects on the normal-mode displacements in terms of the solvent local field lead are complicated by the effect of the solvent on the structure of the complex. We propose that in CH{sub 2}Cl{sub 2} but not in CCl{sub 4}, the complex adopts a low-symmetry ground-state geometry which permits vibronic coupling of the charge-transfer and locally excited (TCNE) states. 33 refs., 7 figs., 4 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 50501
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 17 Vol. 99; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
99 GENERAL AND MISCELLANEOUS
ABSORPTION SPECTRA
ALKYLATED AROMATICS
BINDING ENERGY
COMPLEXES
DIPOLE MOMENTS
ELECTRONS
ETHYLENE
EXCITED STATES
GROUND STATES
MATHEMATICAL MODELS
PHYSICAL PROPERTIES
RAMAN SPECTRA
SOLVENTS
TOLUENE
VALENCE