Theoretical analysis of the third-order nonlinear optical properties of linear cyanines and polyenes

Brian M. Pierce

doi:10.1117/12.50714

1 December 1991 Theoretical analysis of the third-order nonlinear optical properties of linear cyanines and polyenes

Brian M. Pierce

Proceedings Volume 1560, Nonlinear Optical Properties of Organic Materials IV; (1991) https://doi.org/10.1117/12.50714
Event: San Diego, '91, 1991, San Diego, CA, United States

Abstract

The nonresonant (pi) -electronic component of (gamma) (- 3(omega) ;(omega) ,(omega) ,(omega) ), (gamma) (pi) , is calculated for all-trans, linear symmetric cyanine, and streptocyanine cations with no double-single bond-length alternation, and for cyanine cations with asymmetric geometries resulting from the artificial imposition of double-single bond-length alternation. These (gamma) (pi) are compared with those previously calculated for all-trans linear polyenes with double-single bond-length alternation, and for a new set calculated with geometries resulting from the artificial imposition of no double-single bond-length alternation. Bond-length alternation is found to dramatically affect (gamma) (pi) for the linear cyanines: the (gamma) (pi) for the symmetric cyanines are calculated to be negative; the (gamma) (pi) for the asymmetric cyanines change from negative to positive with increasing chain length. The (gamma) (pi) for the linear polyenes are always positive regardless of the extent of bond-length alternation; the (gamma) (pi) for the linear polyenes increase with decreasing bond-length alternation. The (gamma) (pi) for the symmetric linear cyanines increase more rapidly with the number of (pi) -electrons than the (gamma) (pi) for the linear polyenes: (gamma) (pi) (symmetric cyanines) varies as N(pi -e)8 and (gamma) (pi) (linear polyenes) varies as N(pi -e)4, where Npi-e equals 4, 6, 8, 10, 12. The (gamma xxxx component along the chain axis is the most dominant one of (gamma) (pi) for all linear molecules studied. The salient 1(pi) (pi) * states and the important terms in the sum-over-states expression that define (gamma) xxxx, and hence (gamma) (pi) , are identified for the molecules. The dependence of (gamma) (pi) and (beta) (pi) on the geometric asymmetry of a pentamethine cyanine cation is investigated. The polymethines in general, and the cyanines in particular, comprise a very interesting class of nonlinear optical, (pi) -electron molecules that merit further experimental study.

Citation Download Citation

Brian M. Pierce "Theoretical analysis of the third-order nonlinear optical properties of linear cyanines and polyenes", Proc. SPIE 1560, Nonlinear Optical Properties of Organic Materials IV, (1 December 1991); https://doi.org/10.1117/12.50714

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