From owner-chemistry /at\ccl.net Sat Apr 24 07:02:00 2021 From: "Igors Mihailovs igorsm() cfi.lu.lv" 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 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" 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 Dear Mr=2E Yao,

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

Bes= t regards,
Igors Mihailovs

On 24 April 2021 05:56:21 EEST, "sw yao igors2003/a163=2Ecom" <owner-ch= emistry~~ccl=2Enet> wrote:


Sent to CCL by: "sw  yao" [igors2003(!)163=2Ecom=
]
I am doing the chemical reactivity study, molecular orbitals being inv=
olved=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 b=
e identical=2E However, the two turn out not 
the saame: taking  hydroge=
n molecule ion as an example, calculated by Gaussian, the 
resultant Foc=
k 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



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Sent from my Android = device with K-9 Mail=2E Please excuse my brevity=2E ------6KDAVCTTCXPF0IJMW6MOUST03WF071--