In the case of natural orbitals, the printed energies are the diagonal elements of the effective fock matrix in the basis of natural orbitals. In the case of canonical orbitals, they are the eigenvalues of the fock matrix, and the occupation numbers are the diagonal elements of the density matrix in the canonical orbital basis.
In general, whatever orbital basis you have, the "orbital energies" are the diagonal elements of the fock matrix and the "occupation numbers" the diagonal elements of the density matrix. H.-J. Werner ----- Forwarded message from Nathan DeYonker <[EMAIL PROTECTED]> ----- From: "Nathan DeYonker" <[EMAIL PROTECTED]> To: <[EMAIL PROTECTED]> Subject: [molpro-user] MCSCF orbital energies? Date: Thu, 11 Nov 2004 11:43:23 -0500 (EST) Message-ID: <[EMAIL PROTECTED]> X-Mailer: SquirrelMail (version 1.2.10) This question has been proposed a few times in the mailing list without a public response: If a multi is run and the MCSCF natural orbitals are printed, energy eigenvalues of the NOs are given. How are these energies being calculated? Diagonalization of the 1-e density matrix should not give orbital energies... Thanks Nate -------------------------------------------------- Nathan DeYonker | phone: 706-542-7737 Ctr. for Comp. Chemistry | fax: 706 542-0406 University of Georgia | email:[EMAIL PROTECTED] Athens, GA 30602-2556 | http://www.ccc.uga.edu -------------------------------------------------- ----- End forwarded message ----- -- Prof. Hans-Joachim Werner Institute for Theoretical Chemistry University of Stuttgart Pfaffenwaldring 55 D-70569 Stuttgart, Germany Tel.: (0049) 711 / 685 4400 Fax.: (0049) 711 / 685 4442 e-mail: [EMAIL PROTECTED]
