<html><head><meta http-equiv="Content-Type" content="text/html; charset=utf-8"></head><body style="word-wrap: break-word; -webkit-nbsp-mode: space; line-break: after-white-space;" class="">Dear Kha Trinh, <div class=""><br class=""></div><div class="">the results of population analyses such as Mulliken population analysis and charge analyses such as Hirscheld and DDEC charges are </div><div class="">not unique and may severely differ - in some cases even within the sign! As such the differences you observe are within what to expect. </div><div class=""><br class=""></div><div class="">Best regards, </div><div class="">Thomas Kühne<br class=""><div><br class=""><blockquote type="cite" class=""><div class="">Am 14.01.2025 um 02:21 schrieb Kha Trinh <<a href="mailto:minhkha010301@gmail.com" class="">minhkha010301@gmail.com</a>>:</div><br class="Apple-interchange-newline"><div class=""><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Dear CP2K Users,<br class=""></font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">I’m working on the geometry optimization of a transition state featuring an <strong class="">O--Li--O</strong> structure using CP2K and ASE. As part of the analysis, I calculated Mulliken and Hirshfeld charges, but I noticed significant discrepancies between the two methods.</font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Here are the results for two cases of the transition state:</font></p><p style="caret-color: rgb(0, 0, 0);" class=""><strong class=""><font face="Times New Roman" size="2" class="">Mulliken Charges:</font></strong></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Oxygen (O): -0.361</font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Lithium (Li): <span style="" class="">0.565</span></font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Oxygen (O): -0.367<span style="" class=""><br class=""></span></font></p><p style="caret-color: rgb(0, 0, 0);" class=""><strong class=""><font face="Times New Roman" size="2" class="">Hirshfeld Charges</font></strong></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Oxygen (O): -0.261</font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Lithium (Li): -0.470</font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Oxygen (O): -0.265<br class=""></font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">The results from Mulliken and Hirshfeld methods show opposite trends regarding the charge on the Li atom. The Hirshfeld analysis, in particular, seems counterintuitive because I would expect lithium, located between two oxygen atoms, to have a partially positive charge. However, in my field, it is more common to report Mulliken charges.</font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Could this discrepancy arise from the charge partitioning methods or my calculation settings? My system includes C, H, O, N, and Li atoms, using the DZVP-GTH basis set and GTH-PBE functional. Any advice on interpreting or validating these results would be greatly appreciated. I have attached the relevant input and output files for reference. </font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Thank you so much in advance</font></p><p style="caret-color: rgb(0, 0, 0);" class=""><font face="Times New Roman" size="2" class="">Best regards,<br class="">Kha</font></p><div class=""><br class="webkit-block-placeholder"></div>
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