[molpro-user] Calculation of the properties of the outermost electron of an atom

sasha medvedev vinsanity305 at mail.ru
Thu Mar 13 20:38:20 GMT 2014

 Hello, Tatiana Korona.
Thanks for your advise.

I also noticed in the molpro mailing list (  http://www.molpro.net/pipermail/molpro-user/2014-March/005880.html ), that one can look at contribution of 
each orbital to the matrix element of a one-particle operator with the help of the property program.

Alexander Medvedev

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