[molpro-user] Expectation of second moment and kinetic energy

[Yannis Petousis]

Dear molpro users,

In a simple rhf calculation of around 50 atoms, I am trying to find the expectation values of kinetic energy and second moment of position.
My understanding is that this is done using the respective operators, EKIN and SM.
However, the expectation of the kinetic energy I am getting, violates the virial theorem and the expectation of the second moment components are negative!

Here is my input:
{hf;
start,2100.2;
wf,250,1,0;
expec,pot,ekin,ov,sm,delta,tm;
}
show,epot,kin,ov,sm,delta,tm;


And here is the output:
!RHF expec            <1.1|XX|1.1>  -532.748689831615
!RHF expec            <1.1|XX|1.1>  -532.748689831615
!RHF expec            <1.1|ZZ|1.1>  -522.658296533770
!RHF expec          <1.1|EKIN|1.1>   122.891738342572


Note: I am using no symmetry so my only state is 1.1 

Can anyone help?

Thank you,
Yannis

Ioannis Petousis
PhD Student
Nanoscale Prototyping Laboratory
Mechanical Engineering dpt.
Stanford University
email: petousis at stanford.edu