On the effects of spinorbit coupling on molecular properties: Dipole moment and polarizability of PbO and spectroscopic constants for the ground and excited states
(2004) In Advances in Quantum Chemistry 47. p.3749 Abstract
 The lower electronic states of the molecule PbO have been studied using a newly developed basis set of the atomic natural orbital (ANO) type. The method includes scalar relativistic effects through the use of a DouglasKroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using secondorder perturbation theory (CASSCF/CASPT2). Spinorbit coupling is added a posteriori by means of the RASSCF state interaction (RASSI) method, with all electronic states originating from Pb(s(2)p(2),P3, D1, S1) and O(s(2)p(4), (3)p) included in the Cl expansion. Computed spectroscopic constants for the 0(+) ground level are: Re = 1.926(1.922)angstrom, D0 = 4.00(3.83) eV, omega(e), = 723(721) cm(1), with... (More)
 The lower electronic states of the molecule PbO have been studied using a newly developed basis set of the atomic natural orbital (ANO) type. The method includes scalar relativistic effects through the use of a DouglasKroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using secondorder perturbation theory (CASSCF/CASPT2). Spinorbit coupling is added a posteriori by means of the RASSCF state interaction (RASSI) method, with all electronic states originating from Pb(s(2)p(2),P3, D1, S1) and O(s(2)p(4), (3)p) included in the Cl expansion. Computed spectroscopic constants for the 0(+) ground level are: Re = 1.926(1.922)angstrom, D0 = 4.00(3.83) eV, omega(e), = 723(721) cm(1), with experimental data within parentheses. Corresponding data for the 11 lowest excited levels are also presented. The dipole moment for the ground state has been computed to be 1.73(1.83) a.u. using finite field perturbation theory. The effect of spinorbit coupling is to reduce the value with 0.03 a.u. This illustrative calculation shows that an approach that adds scalar relativistic effects to a nonrelativistic wave function, and treats spinorbit coupling by a configuration interaction method, can be used to obtain accurate properties also for molecules containing heavy main group elements. (Less)
Please use this url to cite or link to this publication:
http://lup.lub.lu.se/record/247272
 author
 Roos, Björn ^{LU} and Malmqvist, PerÅke ^{LU}
 organization
 publishing date
 2004
 type
 Contribution to journal
 publication status
 published
 subject
 in
 Advances in Quantum Chemistry
 volume
 47
 pages
 37  49
 publisher
 Elsevier
 external identifiers

 wos:000228024400003
 scopus:19944405553
 ISSN
 00653276
 DOI
 10.1016/S00653276(04)470038
 language
 English
 LU publication?
 yes
 id
 b2815ded54924fd0ad9bef3d0467ff16 (old id 247272)
 date added to LUP
 20071031 09:20:46
 date last changed
 20180107 09:21:33
@article{b2815ded54924fd0ad9bef3d0467ff16, abstract = {The lower electronic states of the molecule PbO have been studied using a newly developed basis set of the atomic natural orbital (ANO) type. The method includes scalar relativistic effects through the use of a DouglasKroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using secondorder perturbation theory (CASSCF/CASPT2). Spinorbit coupling is added a posteriori by means of the RASSCF state interaction (RASSI) method, with all electronic states originating from Pb(s(2)p(2),P3, D1, S1) and O(s(2)p(4), (3)p) included in the Cl expansion. Computed spectroscopic constants for the 0(+) ground level are: Re = 1.926(1.922)angstrom, D0 = 4.00(3.83) eV, omega(e), = 723(721) cm(1), with experimental data within parentheses. Corresponding data for the 11 lowest excited levels are also presented. The dipole moment for the ground state has been computed to be 1.73(1.83) a.u. using finite field perturbation theory. The effect of spinorbit coupling is to reduce the value with 0.03 a.u. This illustrative calculation shows that an approach that adds scalar relativistic effects to a nonrelativistic wave function, and treats spinorbit coupling by a configuration interaction method, can be used to obtain accurate properties also for molecules containing heavy main group elements.}, author = {Roos, Björn and Malmqvist, PerÅke}, issn = {00653276}, language = {eng}, pages = {3749}, publisher = {Elsevier}, series = {Advances in Quantum Chemistry}, title = {On the effects of spinorbit coupling on molecular properties: Dipole moment and polarizability of PbO and spectroscopic constants for the ground and excited states}, url = {http://dx.doi.org/10.1016/S00653276(04)470038}, volume = {47}, year = {2004}, }