Density Functional Studies of the Dipole Polarizabilities of Substituted Stilbene, Azoarene and Related Push-Pull Molecules

International Journal of Molecular Sciences

Alan Hinchliffe¹  Beatrice Nikolaidi¹ 

[1] The University of Manchester, School of Chemistry (North Campus), Sackville Street, Manchester M60 1QD, UK.

关键词: Ab Initio;    Miller indices;    AM1;    dipole polarizability;    QSAR;    Stilbene;    azoarene;    push-pull mechanism;   

DOI  :  10.3390/i5050224

来源: mdpi

【 摘 要 】

We report high quality B3LYP Ab Initio studies of the electric dipole polarizability of three related series of molecules: para-XC₆H₄Y, XC₆H₄CH=CHC₆H₄Y and XC₆H₄N=NC₆H₄Y, where X and Y represent H together with the six various activating through deactivating groups NH₂, OH, OCH_3, CHO, CN and NO₂. Molecules for which X is activating and Y deactivating all show an enhancement to the mean polarizability compared to the unsubstituted molecule, in accord with the order given above. A number of representative Ab Initio calculations at different levels of theory are discussed for azoarene; all subsequent Ab Initio polarizability calculations were done at the B3LYP/6-311G(2d,1p)//B3LYP/6-311++G(2d,1p) level of theory.

We also consider semi-empirical polarizability and molecular volume calculations at the AM1 level of theory together with QSAR-quality empirical polarizability calculations using Miller’s scheme. Least-squares correlations between the various sets of results show that these less costly procedures are reliable predictors of <α> for the first series of molecules, but less reliable for the larger molecules.

【 授权许可】

CC BY   
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