From owner-chemistry@ccl.net Sat Apr 24 06:27:01 2021 From: "Brian Salter-Duke brian.james.duke-,-gmail.com" 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 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
The hydrogen=C2=A0molecule 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=C2=A0 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 <= br> interaction with other electrons. Along this line, I believe, for any one-e= lectron
system, the Fock and Hamitonian should be identical. However, the two turn = out not
the saame: taking=C2=A0 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



-=3D This is automatically added to each message by the mailing script =3D-=
E-mail to subscribers: CHEMISTRY- -ccl.net or use:
=C2=A0 =C2=A0 =C2=A0 http://www.ccl.net/cgi-bin/ccl/s= end_ccl_message

E-mail to administrators: CHEMISTRY-REQUEST- -ccl.net or use
=C2=A0 =C2=A0 =C2=A0 http://www.ccl.net/cgi-bin/ccl/s= end_ccl_message
=C2=A0 =C2=A0 =C2=A0 http://www.ccl.net/chemistry/sub_un= sub.shtml

Before posting, check wait time at: http://www.ccl.net

Job: http://www.ccl.net/jobs
Conferences: http://server.ccl.net/chemist= ry/announcements/conferences/

Search Messages: http://www.ccl.net/chemistry/sear= chccl/index.shtml
=C2=A0 =C2=A0 =C2=A0 http://www.ccl.net/spammers.txt

RTFI: http://www.ccl.net/chemistry/aboutccl/ins= tructions/




--
Brian Salter-Duke (aka Brian Duke)
Brian.James.Duke- -gmai= l.com
--0000000000008358b605c0b43da5-- From owner-chemistry@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



-=3D This is automatically added to each message by t=
he 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 heade=
r=2E

E-mail to subscribers: CHEMISTRY~~ccl=2Enet or use:
      http://www=2Ec=
cl=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_cc=
l_message
      http://www=2Eccl=2Enet/chemistry/=
sub_unsub=2Eshtml

Before posting, check wait time at: http://www=2Eccl=2Enet

Job: http://www=2Eccl=2Enet/jobs 
Conference=
s: http://server=2Eccl=2Enet/chemistry/announcements/conferences/
Search Messages: http://www=2Eccl=2Enet/chemistry/searchccl/index=2Eshtml
If your mail bounces from CCL with 5=2E7=2E1 error, check:
      <=
a href=3D"http://www=2Eccl=2Enet/spammers=2Etxt">http://www=2Eccl=2Enet/spa=
mmers=2Etxt

RTFI: http://www=2Eccl=2Enet/chemistry/aboutccl/instruction=
s/



--
Sent from my Android = device with K-9 Mail=2E Please excuse my brevity=2E ------6KDAVCTTCXPF0IJMW6MOUST03WF071-- From owner-chemistry@ccl.net Sat Apr 24 08:17:00 2021 From: "Igors Mihailovs igorsm[-]cfi.lu.lv" 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 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" 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 Me fool=2E The talk was about the ONE-ELECTRON Ham= iltonian=2E

Thank You, Dr=2E Salter-Duke!

Best regards,
Ig= ors Mihailovs


On 24 April 2021 12:07:= 11 EEST, "Brian Salter-Duke brian=2Ejames=2Eduke-,-gmail=2Ecom" <owner-c= hemistry^_^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 involve= d=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 on= e-electron
system, the Fock and Hamitonian should be identical=2E However, the two tu= rn 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 kn= ow where it
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= -
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
      http://www=2Eccl=2Enet/chemi= stry/sub_unsub=2Eshtml

Before posting, check wait time at: http://www=2Eccl=2Enet

Job: http://www=2Eccl=2Enet/jobs
Conferences: http://server=2Eccl=2Ene= t/chemistry/announcements/conferences/

Search Messages: http://www=2Eccl=2Enet/che= mistry/searchccl/index=2Eshtml
      http://www=2Eccl=2Enet/spammers=2Etxt=

RTFI: http://www=2Eccl=2Enet/chemistry/about= ccl/instructions/




--
Brian Salter-D= uke (aka Brian Duke)
Brian=2EJames=2EDuke%%gmail=2Ecom

--
Sent from my Android device with K-9 Mail=2E= Please excuse my brevity=2E ------RNRZQ8ZIWKBGUYETEW20U8TADDZADJ--