Re: CCL:Defining orbitals

["Derosa-Latech" <pderosa :: latech.edu>]

I am puzzled by the question. If I understand correctly, by constraining electrons to particular atomic orbitals, you already define a wave function which is now not a result of your calculation and thus may or may not be a solution of the Schrödinger equation (what is an eigenvalue problem).  What is it that you want to do, get the energy of the system in that particular state?

 

 

----- Original Message -----

From: Wayne Steinmetz

To: chemistry :: ccl.net

Sent: Friday, June 10, 2005 3:45 PM

Subject: CCL:Defining orbitals

The electrons belong to the entire atom and are not constrained to any orbital.  One uses orbitals to construct the wave function.  One must be sure that the set of orbitals, i.e. the basis set, is sufficiently flexible to describe completely the molecular species.  You are dealing with an atomic species so a polarization basis set is probably not needed.

 

Wayne E. Steinmetz

Carnegie Professor of Chemistry

Woodbadge Course Director

Chemistry Department

Pomona College

645 North College Avenue

Claremont, California 91711-6338

USA

phone: 1-909-621-8447

FAX: 1-909-707-7726

Email: wsteinmetz :: pomona.edu

WWW: pages.pomona.edu/~wsteinmetz

 

-----Original Message-----
From: Computational Chemistry List [mailto:chemistry-request :: ccl.net] On Behalf Of Christopher Thompson
Sent: Thursday, June 09, 2005 6:09 PM
To: chemistry :: ccl.net
Subject: CCL:Defining orbitals

 

Gday,

 

I would like to do an MP2 calc on a Li- species in triplet state.

 

With one electron in the s orbital and one in a p orbital,

how can you constrain the electron to say the px orbital?

 

Cheers,

cdth :: unimelb.edu.au

 

Christopher Thompson

Laser Spectroscopy Group

School of Chemistry

University of Melbourne