Anharmonic force fields of perchloric acid, HClO4_4, and perchloric anhydride, Cl2_2O7_7. An extreme case of inner polarization

DFT (density functional theory) anharmonic force fields with basis sets near the Kohn-Sham limit have been obtained for perchloric acid, HClO$_4$, and perchloric anhydride, Cl$_2$O$_7$. Calculated fundamental frequencies are in very good agreement with available experimental data. Some reassignments in the vibrational spectra of Cl$_2$O$_7$ are proposed based on our calculations. HClO$_4$ and Cl$_2$O$_7$ are particularly severe examples of the `inner polarization' phenomenon. The polarization consistent basis sets pc-1 and pc-2 (as well as their augmented counterparts) should be supplemented with two (preferably three) and one (preferably two) high-exponent $d$ functions, respectively, on second-row atoms. Complete anharmonic force fields are available as electronic supporting information.Comment: J. Mol. Struct., in press (special issue); Electronic Supporting Information at http://theochem.weizmann.ac.il/web/papers/Cl2O7.htm

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