From owner-chemistry@ccl.net Mon Oct 22 07:19:01 2018 From: "Ulrike Salzner salzner-,-fen.bilkent.edu.tr" To: CCL Subject: CCL: sign of AO coefficients and nodes of orbitals Message-Id: <-53521-181022060734-9806-BQi/b3kuMDxR9NvKKt1zxA]![server.ccl.net> X-Original-From: Ulrike Salzner Content-Type: multipart/alternative; boundary="0000000000007409ce0578ce6b89" Date: Mon, 22 Oct 2018 13:06:49 +0300 MIME-Version: 1.0 Sent to CCL by: Ulrike Salzner [salzner%%fen.bilkent.edu.tr] --0000000000007409ce0578ce6b89 Content-Type: text/plain; charset="UTF-8" Hello, I always thought that the sign changes of the AO or MO coefficients reflect the nodal structure of the atomic orbitals, e.g one sign change for 2s, two for 3s and so on no matter how many basis functions contribute. This seems to be the case with Pople basis sets. At least that's what I saw for any case that I have looked at so far. With Dunning correlation consistent basis sets, the sign changes seem to have nothing to do with the nature of the orbitals, see for example for Mg 2s below which has two sign changes. My thinking was obviously wrong but how can I figure out what orbital I am dealing with, if the coefficients do not tell me? Thanks enlightenment, Ulrike 6-31G* Molecular Orbital Coefficients: 1 2 3 4 5 (A1G)--O (A1G)--O (T1U)--O (T1U)--O (T1U)--O Eigenvalues -- -49.01914 -3.76376 -2.27827 -2.27827 -2.27827 1 1 Mg 1S 0.99741 -0.25504 0.00000 0.00000 0.00000 2 2S 0.01078 1.02972 0.00000 0.00000 0.00000 3 2PX 0.00000 0.00000 0.99510 0.00000 0.00000 4 2PY 0.00000 0.00000 0.00000 0.99510 0.00000 5 2PZ 0.00000 0.00000 0.00000 0.00000 0.99510 aug-cc-pvqz Molecular Orbital Coefficients: 1 2 3 4 5 (A1G)--O (A1G)--O (T1U)--O (T1U)--O (T1U)--O Eigenvalues -- -49.03177 -3.76773 -2.28221 -2.28221 -2.28221 1 1 Mg 1S 1.00047 -0.25370 0.00000 0.00000 0.00000 2 2S -0.00346 0.62949 0.00000 0.00000 0.00000 3 3S -0.00165 -0.42495 0.00000 0.00000 0.00000 4 4S -0.00048 0.01639 0.00000 0.00000 0.00000 5 5S 0.00046 -0.01004 0.00000 0.00000 0.00000 6 6S -0.00022 0.00393 0.00000 0.00000 0.00000 7 7S 0.00005 -0.00084 0.00000 0.00000 0.00000 Prof. Ulrike Salzner Department of Chemistry Bilkent University 06800 Bilkent, Ankara 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