Dear cp2k users and experts,<div><br></div><div>I always find for transition metal composites the Hirshfeld charges of metal atoms are calculated to be negative, however, traditionally according to chemical intuition, metal atoms always have positive charges rather than negative (for example the rutile TiO2, hirshfeld charges of Ti and O are -0.927 and 0.464 respectively, PBE/DZVP-MOLOPT-SR-GTH), while I find for simple molecules Hirshfeld population analysis works well (for example the CO molecule, C has hirshfeld charge 0.212, O has -0.203, PBE/DZVP-MOLOPT-SR-GTH).</div><div><br></div><div>I am worried about whether Hirshfeld population analysis is still illustrative and reliable under transition metal composites circumstances, although I have seen many papers stating that Hirshfeld charges is already the most reliable one among Mulliken, Bader, Lowdin and Hirshfeld.</div><div><br></div><div>Could anyone give me some suggestions or share opinions about reliability of population analysis? Thanks very much.</div><div><br></div><div>Yike</div>
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