From owner-chemistry@ccl.net Sat Apr 24 06:27:01 2021 From: "Brian Salter-Duke brian.james.duke-,-gmail.com" <owner-chemistry**server.ccl.net> To: CCL Subject: CCL:G: the difference between hamitonian and fock matrix Message-Id: <-54309-210424050730-12934-dV8PwI867S3IVPIMw2bkYw**server.ccl.net> X-Original-From: Brian Salter-Duke <brian.james.duke*gmail.com> Content-Type: multipart/alternative; boundary="0000000000008358b605c0b43da5" Date: Sat, 24 Apr 2021 19:07:11 +1000 MIME-Version: 1.0 Sent to CCL by: Brian Salter-Duke [brian.james.duke(!)gmail.com] --0000000000008358b605c0b43da5 Content-Type: text/plain; charset="UTF-8" The hydrogen molecule is a 2-electron system, not a 1-electron system. On Sat, Apr 24, 2021 at 3:31 PM sw yao igors2003/a163.com < owner-chemistry- -ccl.net> wrote: > > Sent to CCL by: "sw yao" [igors2003(!)163.com] > I am doing the chemical reactivity study, molecular orbitals being > involved. Fock > matrix element was assumed the atomic orbital energy, the Hamitonian plus > interaction with other electrons. Along this line, I believe, for any > one-electron > system, the Fock and Hamitonian should be identical. However, the two turn > out not > the saame: taking hydrogen molecule ion as an example, calculated by > Gaussian, the > resultant Fock matrix is quite distinct from the Hamitonian. I do not know > where it > is wrong. Could anyone show me a way out? > S. Yao, igors2003:-:163.com> > > -- Brian Salter-Duke (aka Brian Duke) Brian.James.Duke- -gmail.com --0000000000008358b605c0b43da5 Content-Type: text/html; charset="UTF-8" Content-Transfer-Encoding: quoted-printable <div dir=3D"ltr">The hydrogen=C2=A0molecule is a 2-electron system, not a 1= -electron system.</div><br><div class=3D"gmail_quote"><div dir=3D"ltr" clas= s=3D"gmail_attr">On Sat, Apr 24, 2021 at 3:31 PM sw yao igors2003/<a href= =3D"http://a163.com">a163.com</a> <<a href=3D"mailto:owner-chemistry- -ccl= .net">owner-chemistry- -ccl.net</a>> wrote:<br></div><blockquote class=3D"= gmail_quote" style=3D"margin:0px 0px 0px 0.8ex;border-left:1px solid rgb(20= 4,204,204);padding-left:1ex"><br> Sent to CCL by: "sw=C2=A0 yao" [igors2003(!)<a href=3D"http://163= .com" rel=3D"noreferrer" target=3D"_blank">163.com</a>]<br> I am doing the chemical reactivity study, molecular orbitals being involved= . Fock <br> matrix element was assumed the atomic orbital energy, the Hamitonian plus <= br> interaction with other electrons. Along this line, I believe, for any one-e= lectron <br> system, the Fock and Hamitonian should be identical. However, the two turn = out not <br> the saame: taking=C2=A0 hydrogen molecule ion as an example, calculated by = Gaussian, the <br> resultant Fock matrix is quite distinct from the Hamitonian. I do not know = where it <br> is wrong. Could anyone show me a way out?<br> S. Yao, igors2003:-:<a href=3D"http://163.com" rel=3D"noreferrer" target=3D= "_blank">163.com</a><br> <br> <br> <br> -=3D This is automatically added to each message by the mailing script =3D-= <br<br=<br<br> <br> E-mail to subscribers: <a href=3D"mailto:CHEMISTRY- -ccl.net" target=3D"_blan= k">CHEMISTRY- -ccl.net</a> or use:<br> =C2=A0 =C2=A0 =C2=A0 <a href=3D"http://www.ccl.net/cgi-bin/ccl/send_ccl_mes= sage" rel=3D"noreferrer" target=3D"_blank">http://www.ccl.net/cgi-bin/ccl/s= end_ccl_message</a><br> <br> E-mail to administrators: <a href=3D"mailto:CHEMISTRY-REQUEST- -ccl.net" targ= et=3D"_blank">CHEMISTRY-REQUEST- -ccl.net</a> or use<br> =C2=A0 =C2=A0 =C2=A0 <a href=3D"http://www.ccl.net/cgi-bin/ccl/send_ccl_mes= sage" rel=3D"noreferrer" target=3D"_blank">http://www.ccl.net/cgi-bin/ccl/s= end_ccl_message</a><br> <br<br> =C2=A0 =C2=A0 =C2=A0 <a href=3D"http://www.ccl.net/chemistry/sub_unsub.shtm= l" rel=3D"noreferrer" target=3D"_blank">http://www.ccl.net/chemistry/sub_un= sub.shtml</a><br> <br> Before posting, check wait time at: <a href=3D"http://www.ccl.net" rel=3D"n= oreferrer" target=3D"_blank">http://www.ccl.net</a><br> <br> Job: <a href=3D"http://www.ccl.net/jobs" rel=3D"noreferrer" target=3D"_blan= k">http://www.ccl.net/jobs</a> <br> Conferences: <a href=3D"http://server.ccl.net/chemistry/announcements/confe= rences/" rel=3D"noreferrer" target=3D"_blank">http://server.ccl.net/chemist= ry/announcements/conferences/</a><br> <br> Search Messages: <a href=3D"http://www.ccl.net/chemistry/searchccl/index.sh= tml" rel=3D"noreferrer" target=3D"_blank">http://www.ccl.net/chemistry/sear= chccl/index.shtml</a><br> <br<br> =C2=A0 =C2=A0 =C2=A0 <a href=3D"http://www.ccl.net/spammers.txt" rel=3D"nor= eferrer" target=3D"_blank">http://www.ccl.net/spammers.txt</a><br> <br> RTFI: <a href=3D"http://www.ccl.net/chemistry/aboutccl/instructions/" rel= =3D"noreferrer" target=3D"_blank">http://www.ccl.net/chemistry/aboutccl/ins= tructions/</a><br> <br> <br> </blockquote></div><br clear=3D"all"><div><br></div>-- <br><div dir=3D"ltr"= class=3D"gmail_signature">Brian Salter-Duke (aka Brian Duke)<br><a href=3D= "mailto:Brian.James.Duke- -gmail.com" target=3D"_blank">Brian.James.Duke- -gmai= l.com</a></div> --0000000000008358b605c0b43da5-- From owner-chemistry@ccl.net Sat Apr 24 07:02:00 2021 From: "Igors Mihailovs igorsm() cfi.lu.lv" <owner-chemistry(!)server.ccl.net> To: CCL Subject: CCL:G: the difference between hamitonian and fock matrix Message-Id: <-54310-210424062811-11045-fzytWdi9mKuanKmMLKh7gg(!)server.ccl.net> X-Original-From: Igors Mihailovs <igorsm%a%cfi.lu.lv> Content-Transfer-Encoding: 7bit Content-Type: multipart/alternative; boundary="----6KDAVCTTCXPF0IJMW6MOUST03WF071" Date: Sat, 24 Apr 2021 13:27:53 +0300 MIME-Version: 1.0 Sent to CCL by: Igors Mihailovs [igorsm^_^cfi.lu.lv] ------6KDAVCTTCXPF0IJMW6MOUST03WF071 Content-Type: text/plain; charset=utf-8 Content-Transfer-Encoding: quoted-printable Dear Mr=2E Yao, I think You are missing the fact that the overlap matrix is non-identity o= ne in real-world calculations because (at least for polyatomic molecules) t= he basis set is not completely orthogonal=2E Maybe for a single atom and mi= nimal basis they would be equal (I think so but please correct me somebody = if I am wrong)=2E Best regards, Igors Mihailovs On 24 April 2021 05:56:21 EEST, "sw yao igors2003/a163=2Ecom" <owner-chemi= stry~~ccl=2Enet> wrote: > >Sent to CCL by: "sw yao" [igors2003(!)163=2Ecom] >I am doing the chemical reactivity study, molecular orbitals being >involved=2E Fock=20 >matrix element was assumed the atomic orbital energy, the Hamitonian >plus=20 >interaction with other electrons=2E Along this line, I believe, for any >one-electron=20 >system, the Fock and Hamitonian should be identical=2E However, the two >turn out not=20 >the saame: taking hydrogen molecule ion as an example, calculated by >Gaussian, the=20 >resultant Fock matrix is quite distinct from the Hamitonian=2E I do not >know where it=20 >is wrong=2E Could anyone show me a way out? >S=2E Yao, igors2003:-:163=2Ecom > > > >-=3D This is automatically added to each message by the mailing script = =3D- >To recover the email address of the author of the message, please >change >the strange characters on the top line to the ~~ sign=2E You can also >look up the X-Original-From: line in the mail header=2E > >E-mail to subscribers: CHEMISTRY~~ccl=2Enet or use: > http://www=2Eccl=2Enet/cgi-bin/ccl/send_ccl_message > >E-mail to administrators: CHEMISTRY-REQUEST~~ccl=2Enet or use > http://www=2Eccl=2Enet/cgi-bin/ccl/send_ccl_message > >Subscribe/Unsubscribe:=20 > http://www=2Eccl=2Enet/chemistry/sub_unsub=2Eshtml > >Before posting, check wait time at: http://www=2Eccl=2Enet > >Job: http://www=2Eccl=2Enet/jobs=20 >Conferences: http://server=2Eccl=2Enet/chemistry/announcements/conference= s/ > >Search Messages: http://www=2Eccl=2Enet/chemistry/searchccl/index=2Eshtml > >If your mail bounces from CCL with 5=2E7=2E1 error, check: > http://www=2Eccl=2Enet/spammers=2Etxt > >RTFI: http://www=2Eccl=2Enet/chemistry/aboutccl/instructions/ --=20 Sent from my Android device with K-9 Mail=2E Please excuse my brevity=2E ------6KDAVCTTCXPF0IJMW6MOUST03WF071 Content-Type: text/html; charset=utf-8 Content-Transfer-Encoding: quoted-printable <html><head></head><body>Dear Mr=2E Yao,<br><br>I think You are missing the= fact that the overlap matrix is non-identity one in real-world calculation= s because (at least for polyatomic molecules) the basis set is not complete= ly orthogonal=2E Maybe for a single atom and minimal basis they would be eq= ual (I think so but please correct me somebody if I am wrong)=2E<br><br>Bes= t regards,<br>Igors Mihailovs<br><br><br><br><br><div class=3D"gmail_quote"= >On 24 April 2021 05:56:21 EEST, "sw yao igors2003/a163=2Ecom" <owner-ch= emistry~~ccl=2Enet> wrote:<blockquote class=3D"gmail_quote" style=3D"marg= in: 0pt 0pt 0pt 0=2E8ex; border-left: 1px solid rgb(204, 204, 204); padding= -left: 1ex;"> <pre class=3D"k9mail"><br>Sent to CCL by: "sw yao" [igors2003(!)163=2Ecom= ]<br>I am doing the chemical reactivity study, molecular orbitals being inv= olved=2E Fock <br>matrix element was assumed the atomic orbital energy, the= Hamitonian plus <br>interaction with other electrons=2E Along this line, I= believe, for any one-electron <br>system, the Fock and Hamitonian should b= e identical=2E However, the two turn out not <br>the saame: taking hydroge= n molecule ion as an example, calculated by Gaussian, the <br>resultant Foc= k matrix is quite distinct from the Hamitonian=2E I do not know where it <b= r>is wrong=2E Could anyone show me a way out?<br>S=2E Yao, igors2003:-:163= =2Ecom<br><br><br><br>-=3D This is automatically added to each message by t= he mailing script =3D-<br>To recover the email address of the author of the= message, please change<br>the strange characters on the top line to the ~~ = sign=2E You can also<br>look up the X-Original-From: line in the mail heade= r=2E<br><br>E-mail to subscribers: CHEMISTRY~~ccl=2Enet or use:<br> <a = href=3D"http://www=2Eccl=2Enet/cgi-bin/ccl/send_ccl_message">http://www=2Ec= cl=2Enet/cgi-bin/ccl/send_ccl_message</a><br><br>E-mail to administrators: = CHEMISTRY-REQUEST~~ccl=2Enet or use<br> <a href=3D"http://www=2Eccl=2En= et/cgi-bin/ccl/send_ccl_message">http://www=2Eccl=2Enet/cgi-bin/ccl/send_cc= l_message</a><br><br<br> <a href=3D"http://www= =2Eccl=2Enet/chemistry/sub_unsub=2Eshtml">http://www=2Eccl=2Enet/chemistry/= sub_unsub=2Eshtml</a><br><br>Before posting, check wait time at: <a href=3D= "http://www=2Eccl=2Enet">http://www=2Eccl=2Enet</a><br><br>Job: <a href=3D"= http://www=2Eccl=2Enet/jobs">http://www=2Eccl=2Enet/jobs</a> <br>Conference= s: <a href=3D"http://server=2Eccl=2Enet/chemistry/announcements/conferences= /">http://server=2Eccl=2Enet/chemistry/announcements/conferences/</a><br><b= r>Search Messages: <a href=3D"http://www=2Eccl=2Enet/chemistry/searchccl/in= dex=2Eshtml">http://www=2Eccl=2Enet/chemistry/searchccl/index=2Eshtml</a><b= r><br>If your mail bounces from CCL with 5=2E7=2E1 error, check:<br> <= a href=3D"http://www=2Eccl=2Enet/spammers=2Etxt">http://www=2Eccl=2Enet/spa= mmers=2Etxt</a><br><br>RTFI: <a href=3D"http://www=2Eccl=2Enet/chemistry/ab= outccl/instructions/">http://www=2Eccl=2Enet/chemistry/aboutccl/instruction= s/</a><br><br><br></pre></blockquote></div><br>-- <br>Sent from my Android = device with K-9 Mail=2E Please excuse my brevity=2E</body></html> ------6KDAVCTTCXPF0IJMW6MOUST03WF071-- From owner-chemistry@ccl.net Sat Apr 24 08:17:00 2021 From: "Igors Mihailovs igorsm[-]cfi.lu.lv" <owner-chemistry:server.ccl.net> To: CCL Subject: CCL:G: the difference between hamitonian and fock matrix Message-Id: <-54311-210424081527-13997-bgj50NKoteMqZ8yukoU1Tg:server.ccl.net> X-Original-From: Igors Mihailovs <igorsm[-]cfi.lu.lv> Content-Transfer-Encoding: 7bit Content-Type: multipart/alternative; boundary="----RNRZQ8ZIWKBGUYETEW20U8TADDZADJ" Date: Sat, 24 Apr 2021 15:15:15 +0300 MIME-Version: 1.0 Sent to CCL by: Igors Mihailovs [igorsm[#]cfi.lu.lv] ------RNRZQ8ZIWKBGUYETEW20U8TADDZADJ Content-Type: text/plain; charset=utf-8 Content-Transfer-Encoding: quoted-printable Me fool=2E The talk was about the ONE-ELECTRON Hamiltonian=2E Thank You, Dr=2E Salter-Duke! Best regards, Igors Mihailovs On 24 April 2021 12:07:11 EEST, "Brian Salter-Duke brian=2Ejames=2Eduke-,-= gmail=2Ecom" <owner-chemistry^_^ccl=2Enet> wrote: >The hydrogen molecule is a 2-electron system, not a 1-electron system=2E > >On Sat, Apr 24, 2021 at 3:31 PM sw yao igors2003/a163=2Ecom < >owner-chemistry%%ccl=2Enet> wrote: > >> >> Sent to CCL by: "sw yao" [igors2003(!)163=2Ecom] >> I am doing the chemical reactivity study, molecular orbitals being >> involved=2E Fock >> matrix element was assumed the atomic orbital energy, the Hamitonian >plus >> interaction with other electrons=2E Along this line, I believe, for any >> one-electron >> system, the Fock and Hamitonian should be identical=2E However, the two >turn >> out not >> the saame: taking hydrogen molecule ion as an example, calculated by >> Gaussian, the >> resultant Fock matrix is quite distinct from the Hamitonian=2E I do not >know >> where it >> is wrong=2E Could anyone show me a way out? >> S=2E Yao, igors2003:-:163=2Ecom> >> >> > >--=20 >Brian Salter-Duke (aka Brian Duke) >Brian=2EJames=2EDuke%%gmail=2Ecom --=20 Sent from my Android device with K-9 Mail=2E Please excuse my brevity=2E ------RNRZQ8ZIWKBGUYETEW20U8TADDZADJ Content-Type: text/html; charset=utf-8 Content-Transfer-Encoding: quoted-printable <html><head></head><body>Me fool=2E The talk was about the ONE-ELECTRON Ham= iltonian=2E<br><br>Thank You, Dr=2E Salter-Duke!<br><br>Best regards,<br>Ig= ors Mihailovs<br><br><br><div class=3D"gmail_quote">On 24 April 2021 12:07:= 11 EEST, "Brian Salter-Duke brian=2Ejames=2Eduke-,-gmail=2Ecom" <owner-c= hemistry^_^ccl=2Enet> wrote:<blockquote class=3D"gmail_quote" style=3D"mar= gin: 0pt 0pt 0pt 0=2E8ex; border-left: 1px solid rgb(204, 204, 204); paddin= g-left: 1ex;"> <div dir=3D"ltr">The hydrogen molecule is a 2-electron system, not a = 1-electron system=2E</div><br><div class=3D"gmail_quote"><div dir=3D"ltr" c= lass=3D"gmail_attr">On Sat, Apr 24, 2021 at 3:31 PM sw yao igors2003/<a hre= f=3D"http://a163=2Ecom">a163=2Ecom</a> <<a href=3D"mailto:owner-chemistr= y%%ccl=2Enet">owner-chemistry%%ccl=2Enet</a>> wrote:<br></div><blockquot= e class=3D"gmail_quote" style=3D"margin:0px 0px 0px 0=2E8ex;border-left:1px= solid rgb(204,204,204);padding-left:1ex"><br> Sent to CCL by: "sw yao" [igors2003(!)<a href=3D"http://163=2Ecom" r= el=3D"noreferrer" target=3D"_blank">163=2Ecom</a>]<br> I am doing the chemical reactivity study, molecular orbitals being involve= d=2E Fock <br> matrix element was assumed the atomic orbital energy, the Hamitonian plus = <br> interaction with other electrons=2E Along this line, I believe, for any on= e-electron <br> system, the Fock and Hamitonian should be identical=2E However, the two tu= rn out not <br> the saame: taking hydrogen molecule ion as an example, calculated by= Gaussian, the <br> resultant Fock matrix is quite distinct from the Hamitonian=2E I do not kn= ow where it <br> is wrong=2E Could anyone show me a way out?<br> S=2E Yao, igors2003:-:<a href=3D"http://163=2Ecom" rel=3D"noreferrer" targ= et=3D"_blank">163=2Ecom</a><br> <br> <br> <br> -=3D This is automatically added to each message by the mailing script =3D= -<br<br=3D<br<br> <br> E-mail to subscribers: <a href=3D"mailto:CHEMISTRY%%ccl=2Enet" target=3D"_= blank">CHEMISTRY%%ccl=2Enet</a> or use:<br> <a href=3D"http://www=2Eccl=2Enet/cgi-bin/ccl/send_cc= l_message" rel=3D"noreferrer" target=3D"_blank">http://www=2Eccl=2Enet/cgi-= bin/ccl/send_ccl_message</a><br> <br> E-mail to administrators: <a href=3D"mailto:CHEMISTRY-REQUEST%%ccl=2Enet" = target=3D"_blank">CHEMISTRY-REQUEST%%ccl=2Enet</a> or use<br> <a href=3D"http://www=2Eccl=2Enet/cgi-bin/ccl/send_cc= l_message" rel=3D"noreferrer" target=3D"_blank">http://www=2Eccl=2Enet/cgi-= bin/ccl/send_ccl_message</a><br> <br<br> <a href=3D"http://www=2Eccl=2Enet/chemistry/sub_unsub= =2Eshtml" rel=3D"noreferrer" target=3D"_blank">http://www=2Eccl=2Enet/chemi= stry/sub_unsub=2Eshtml</a><br> <br> Before posting, check wait time at: <a href=3D"http://www=2Eccl=2Enet" rel= =3D"noreferrer" target=3D"_blank">http://www=2Eccl=2Enet</a><br> <br> Job: <a href=3D"http://www=2Eccl=2Enet/jobs" rel=3D"noreferrer" target=3D"= _blank">http://www=2Eccl=2Enet/jobs</a> <br> Conferences: <a href=3D"http://server=2Eccl=2Enet/chemistry/announcements/= conferences/" rel=3D"noreferrer" target=3D"_blank">http://server=2Eccl=2Ene= t/chemistry/announcements/conferences/</a><br> <br> Search Messages: <a href=3D"http://www=2Eccl=2Enet/chemistry/searchccl/ind= ex=2Eshtml" rel=3D"noreferrer" target=3D"_blank">http://www=2Eccl=2Enet/che= mistry/searchccl/index=2Eshtml</a><br> <br<br> <a href=3D"http://www=2Eccl=2Enet/spammers=2Etxt" rel= =3D"noreferrer" target=3D"_blank">http://www=2Eccl=2Enet/spammers=2Etxt</a>= <br> <br> RTFI: <a href=3D"http://www=2Eccl=2Enet/chemistry/aboutccl/instructions/" = rel=3D"noreferrer" target=3D"_blank">http://www=2Eccl=2Enet/chemistry/about= ccl/instructions/</a><br> <br> <br> </br<br></br<br></br<br=3D<br<br></blockquote></div><br clear=3D"all"><div= ><br></div>-- <br><div dir=3D"ltr" class=3D"gmail_signature">Brian Salter-D= uke (aka Brian Duke)<br><a href=3D"mailto:Brian=2EJames=2EDuke%%gmail=2Ecom= " target=3D"_blank">Brian=2EJames=2EDuke%%gmail=2Ecom</a></div> </blockquote></div><br>-- <br>Sent from my Android device with K-9 Mail=2E= Please excuse my brevity=2E</body></html> ------RNRZQ8ZIWKBGUYETEW20U8TADDZADJ--