Parameter set "halorg-0-1"

This parametrization for Cl, Br and I is compatible with previous parametrizations for

Repulsive potentials were parametrized for bonds X-C, X-H, X-O, X-N as well as interhalogen bonding.

Note that no repulsive potentials were developed for interactions X-P and X-S;
therefore, molecules with such covalent bonds cannot be described with the current parametrization.

Focus is on the description of halogenated organic molecules. While the C-X interactions have been parametrized on single molecules CH3-X, testing shows that the performance is good for a wide range of organic molecules containing halogen atoms.

Diatomic molecules of halogens are described well, however featuring large
overbinding of up to 30-40 kcal/mol. Molecules containing halogens and oxygen feature a quite large overbinding, too. Still, the geometries are good except for e.g. HXO2. For details, see the referenced article [JCTC2013].

Vibrational frequencies are acceptable as well.  Although a basis set composed of s- and p-orbitals only is used for halogens, the description of these hypervalent molecules is fair, although the atomic charges are overestimated largely.

The performance for molecules containing halogens and nitrogen is slightly better than for the halogen oxides and oxoacids, with an exception being constituted by molecules containing both nitrogen and oxygen atoms.

Relevant publications

[JCTC2013] J. Chem. Theor. Comput. 9, 2939 (2013). [PRB98] Phys. Rev. B 58, 7260 (1998).
[JCTC2011] J. Chem. Theor. Comput. 7, 931 (2011). [JMS01] J. Mol. Struc. (THEOCHEM) 541, 185 (2001).

Publications to be cited

O-N-C-H [PRB98]
S-(O,N,C,H,S) [JMS01]
P-(O,N,C,H,S,P) [JCTC2011]
(Br,Cl,I,F)-* [JCTC2013]

Required sets

The parameters excluding the halogens are generated as in the original mio-1-1 and pbc-0-3 sets. Nevertheless, perform calculations using exclusively parameter files contained in this package, even for pairs of chemical elements for which corresponding parameter files are available in the original sets.  Combination of parameter files from the current set and any previous ones could lead to difficulties in the diagonalizer routine due to different sign convention and small numerical differences in the integrals.

License

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