<HTML><BODY>Hello, Tatiana Korona.<br>Thanks for your advise.<br><br>I also noticed in the molpro mailing list ( <a href="http://www.molpro.net/pipermail/molpro-user/2014-March/005880.html" data-mce-href="http://www.molpro.net/pipermail/molpro-user/2014-March/005880.html" target="_blank">http://www.molpro.net/pipermail/molpro-user/2014-March/005880.html</a> ), that one can look at contribution of <br>each orbital to the matrix element of a one-particle operator with the help of the property program.<br><br>Alexander Medvedev<br><br><br>Thursday, the 6th of march 2014, 21:51 +01:00 from Tatiana Korona <tania@tiger.chem.uw.edu.pl>:<br>
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<div>Hi, Alexander,<br>
<br>
You can make these manipulations through matrop, i.e. load HF orbitals, zero <br>
some of them, make a new "density matrix" and use it to calculate properties. <br>
For the first part, see e.g. <br>
<a href="http://www.molpro.net/pipermail/molpro-user/2012-December/005147.html" target="_blank">http://www.molpro.net/pipermail/molpro-user/2012-December/005147.html</a><br>
Other steps are described well in the manual.<br>
<br>
Best wishes,<br>
<br>
Tatiana<br>
<br>
On Thu, 6 Mar 2014, sasha medvedev wrote:<br>
<br>
> Hello, molpro users.<br>
<br>
Is there any possibility to calculate the root mean square (r.m.s.)<br>
distance of the outermost electron of a particular atom with the help of molpro2010 package?<br>
I faced several problems, when I tried to do it. Here they are:<br>
<br>
1) How can one get the wave function of the outermost electron?<br>
Is it possible in molpro to extract a wave function of a particular electron from the wave function of the atom?<br>
In other words, can I take in molpro2010 one-electron wave function (with the desired set of quantum numbers n,l,m)<br>
from a Slater determinant after restricted/unrestricted-HF routine for an atom?<br>
<br>
2) So, I should calculate the diagonal matrix element of the x^2+y^2+z^2=r^2 one-electron operator,<br>
using a wave function of the outermost electron (i.e. <nlm|r^2|nlm>, where n,l,m - quantum numbers of the outermost electron).<br>
Molpro provides me with the second moment (SM) operator ( <a href="http://www.molpro.net/info/2012.1/doc/manual/node68.html" target="_blank">http://www.molpro.net/info/2012.1/doc/manual/node68.html</a> ).<br>
But it contains summation over all electrons in a system (i.e. SM_{XX} = \sum_{i=1}^{N} x_{i}^{2}, where x_{i} is the x coordinate of the i^{th} electron,<br>
N - total number of electrons in the system).<br>
Will this sum reduce to 1 electron (i.e. SM_{XX}= x_{1}^{2}), when I ask molpro to calculate the expectation value of the<br>
SM operator using wave function of the outermost electron?<br>
<br>
I'm interested in it, because I want to calculate the Le Roy radius ( <a href="http://leroy.uwaterloo.ca/leroy_radius.html" target="_blank">http://leroy.uwaterloo.ca/leroy_radius.html</a> ).<br>
<br>
Alexander Medvedev,<br>
student of the 5th course,<br>
Chemistry department,<br>
Chair of laser chemistry,<br>
MSU<br>
<br>
Dr. Tatiana Korona <a href="http://tiger.chem.uw.edu.pl/staff/tania/index.html" target="_blank">http://tiger.chem.uw.edu.pl/staff/tania/index.html</a><br>
Quantum Chemistry Laboratory<br>
University of Warsaw<br>
Pasteura 1, PL-02-093 Warsaw, POLAND<br>
<br>
`The man who makes no mistakes does not usually make anything.'<br>
Edward John Phelps (1822-1900)<br>
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