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Computational determination of the relative polarizabilities of molecular components
Author(s) -
Jin Ping,
Murray Jane S.,
Politzer Peter
Publication year - 2006
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20974
Subject(s) - molecule , chemistry , transferability , bar (unit) , component (thermodynamics) , atom (system on chip) , inverse , ionization , ionization energy , atomic physics , computational chemistry , physics , thermodynamics , ion , organic chemistry , statistics , meteorology , mathematics , geometry , logit , computer science , embedded system
It is well known that the polarizabilities of both atoms and molecules correlate well with their volumes ( V ). We have shown in earlier work that these relationships can be further improved by including an inverse dependence on the average local ionization energy ( $\bar{I}$ S,ave ) over the surface of the atom or molecule. We have recently suggested that this be extended to the components of molecules (atoms or groups) and that V / $\bar{I}$ S,ave be viewed as a measure of their relative polarizabilities (α i rel ). We have now extended this approach computationally to a total of nine atoms and groups: F, Cl, Br, OH, SH, NH 2 , CH 3 , CN, and NO 2 . The transferability of $\bar{I}$ S,ave , V, and V / $\bar{I}$ S,ave for a given component from one molecule to another is analyzed in detail, and it is shown that components of molecules containing the nitro group are likely to have anomalously low polarizabilities. By converting our α i relto absolute α i via a correlation with Miller's values, we are able to predict the polarizabilities of a large number of molecules. The agreement with available experimental data is quite reasonable (average absolute difference = 0.23 A 3 ), given the inevitable uncertainty associated with the concept of component properties. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006