From owner-chemistry-: at :-ccl.net Thu Feb 22 05:46:01 2007 From: "Xunlei Ding dingxunlei_._gmail.com" To: CCL Subject: CCL:G: G03-Excessive mixing of frozen core and valence orbitals Message-Id: <-33675-070222044031-9414-MmidQXK+hcnisbdZze8wDg*|*server.ccl.net> X-Original-From: Xunlei Ding Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=ISO-8859-1; format=flowed Date: Thu, 22 Feb 2007 10:19:17 +0100 MIME-Version: 1.0 Sent to CCL by: Xunlei Ding [dingxunlei * gmail.com] Dear David, Thank you for your help! Now I found that if it is calculated with "nosymm", everything will be ok. And this is the difference between using key words -Bq and Massage. So I think, for this system, the error is due to symmetry problem. When using symmetry, the calculation is totally wrong. Best regards! Ding Shobe, David David.Shobe*_*sud-chemie.com wrote: >Sent to CCL by: "Shobe, David" [David.Shobe|-|sud-chemie.com] >Ding, > >The Mulliken charges you see on H #7 and F #8 are related to the error message you got earlier. It just means that the basis functions on H #7 and F #8 are being occupied in the calculation. > >What bothers me is the charge of > +7 on F #4. This means that the valence orbitals on F #4 are NOT being used in the wave function!!! You might want to look at the electron density (if you have a suitable visuialization program) to see whether that is strange also. Do you get similar Mulliken charges in a HF calculation? What about other types of charges (NBO, CHELPG, etc.)? > >Regards, >--David Shobe > >-----Original Message----- > > >>From: owner-chemistry_-_ccl.net [mailto:owner-chemistry_-_ccl.net] >> >> >Sent: Tuesday, February 20, 2007 2:59 AM >To: Shobe, David >Subject: CCL:G: G03-Excessive mixing of frozen core and valence orbitals > > >Sent to CCL by: Xunlei Ding [dingxunlei:gmail.com] Dear David, > >Thank you very much for your clear explain and suggestions. > >If this work is done with mp2(fc)/6-311++G**, the error is the same: >" Largest valence mixing into a core orbital is 9.94D-01 Excessive mixing of frozen core and valence orbitals." > >And it finishes successfully with mp2=full, but the energy is very strange, and also the mulliken charge: > > Mulliken atomic charges: > 1 > 1 H -1.463786 > 2 F -0.398420 > 3 H -0.625697 > 4 F 7.487903 > 5 H -1.463786 > 6 F -0.398420 > 7 H -1.625697 > 8 F -1.512097 > >Also mp2(full)/6-311++G** gives strange energy and mulliken charge. > >If the work is done with counterpoise=2 or massage, as suggested by Douglas Fox, everything seems ok (both basis sets, and both mp2-full and mp2-fc). So maybe it is a problem of -bq. > >Best regards! >Ding > >Shobe, David David.Shobe---sud-chemie.com wrote: > > > >>Sent to CCL by: "Shobe, David" [David.Shobe=sud-chemie.com] Because you >>are using ghost atoms, there are empty core orbitals. The HF routine does not distinguish core orbitals from valence orbitals (at least I think this is true), but the MP2 defaults to MP2=FC (frozen core) which of coures does make the distinction. Note that 9.92D-01 = 0.992 = almost full occupancy! >> >>Perhaps using mp2=full would help, but then you'd have to redo any other mp2 calculations (you have to be consistent: either mp2=full everywhere or mp2=fc everywhere). >> >>A larger basis set like 6-311+G* or aug-cc-pVTZ is likely to improve matters. With more valence orbitals to choose from, there is less need to use the core orbital. The 6-31G* basis set is too small for accurate calculations of hydrogen bonding energies anyway, if that's what you're after. Again, you'd have to redo any calculations you've already performed using the smaller basis set. >> >>Regards, >>--David Shobe >> Süd-Chemie, Inc. >> >>Attention to detial is essentail. >> >> >>-----Original Message----- >> >> >> >> >>>From: owner-chemistry=-=ccl.net [mailto:owner-chemistry=-=ccl.net] >>> >>> >>> >>> >>Sent: Sunday, February 18, 2007 8:39 PM >>To: Shobe, David >>Subject: CCL:G: G03-Excessive mixing of frozen core and valence >>orbitals >> >> >>Sent to CCL by: Ding Xunlei [dingxunlei^-^gmail.com] Dear All, >> >>I did a calculation using mp2 and I find an error below. >>Could you give me some suggestion? Thank you! >> >>This input file: >>------------------------------------------------------------ >>#mp2/6-31G* >> >>test >> >>0 1 >> H 0.000000 -0.917747 0.000000 >> F 0.000000 0.000000 0.000000 >> H 0.000000 1.956639 0.000000 >> F 0.000000 2.875828 0.000000 >> H 0.000000 -0.917747 -2.250000 >> F 0.000000 0.000000 -2.250000 >> H-bq 0.000000 1.956639 -2.250000 >> F-bq 0.000000 2.875828 -2.250000 >> >>------------------------------------------------------------ >> >>The output file: >>------------------------------------------------------------------- >>SCF Done: E(RHF) = -199.305447100 A.U. after 21 cycles >> Convg = 0.2272D-08 -V/T = 1.9654 >> S**2 = 0.0000 >>ExpMin= 1.61D-01 ExpMax= 7.00D+03 ExpMxC= 1.05D+03 IAcc=1 IRadAn= >> 1 AccDes= 1.00D-06 >>HarFok: IExCor= 205 AccDes= 1.00D-06 IRadAn= 1 IDoV=1 >>ScaDFX= 1.000000 1.000000 1.000000 1.000000 Largest valence mixing into a core orbital is 9.92D-01 Excessive mixing of frozen core and valence orbitals. >>Error termination via Lnk1e in /gaussian/03d02-xlf10/g03/l801.exe at Sat Feb 17 16:37:03 2007. >> >> >>Yours sincerely, >>Ding Xunlei >>2007-02-19 >>______________________________________________http://www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txtThis e-mail message may contain confidential and / or privileged information. 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