## Semiempirical Calculations of First-Order Hyperpolarizabilities: Testing the Performance of Different Methods in Comparison to Experiment

journal contribution

posted on 22.01.1998 by Bernd Beck, U.-W. Grummt#### journal contribution

Any type of content formally published in an academic journal, usually following a peer-review process.

The performances of three semiempirical program packages for the
calculation of frequency-dependent first-order hyperpolarizabilities are tested using a data set of 200 different
organic compounds. The methods used
are the sum-over-states approaches implemented in VAMP6.0 and CNDOS,
and the time-dependent Hartree−Fock (TDHF) method included in MOPAC. For the configuration
interaction (CI) calculations in the gas-phase single and pair-double excitation (VAMP−PECI) and single
excitation CI (CNDOS−SCI) with two
different sizes of the active orbital window are used. In the case
of MOPAC and VAMP6.0 the AM1 and
PM3 Hamiltonians are used. Although the correlation coefficients,

*r*, obtained are slightly different, all calculational methods are comparably useful for trend predictions in the molecular design of new compounds for nonlinear optical applications. Because of the enormous computational costs, the TDHF method is only feasible for smaller molecules or smaller data sets. To account for solvent effects, the state energies obtained first from gas-phase CI calculations are corrected using the self-consistent-reaction-field (SCRF) approach implemented in VAMP6.0, improving the quality of the results.