New Relativistic Atomic Natural Orbital Basis Sets for Lanthanide Atoms with Applications to the Ce Diatom and LuF3
(2008) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 112(45). p.11431-11435- Abstract
- New basis sets of the atomic natural orbital (ANO) type have been developed for the lanthanide atoms La-Lu. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies and some excitation energies. Computed ionization energies have an accuracy better than 0.1 eV in most cases. Two molecular applications are inluded as illustration: the... (More)
- New basis sets of the atomic natural orbital (ANO) type have been developed for the lanthanide atoms La-Lu. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies and some excitation energies. Computed ionization energies have an accuracy better than 0.1 eV in most cases. Two molecular applications are inluded as illustration: the cerium diatom and the LuF3 molecule. In both cases it is shown that 4f orbitals are not involved in the chemical bond in contrast to an earlier claim for the latter molecule. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1283090
- author
- Roos, Björn LU ; Lindh, Roland LU ; Malmqvist, Per-Åke LU ; Veryazov, Valera LU ; Widmark, Per-Olof LU and Borin, Antonio Carlos
- organization
- publishing date
- 2008
- type
- Contribution to journal
- publication status
- published
- subject
- in
- The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
- volume
- 112
- issue
- 45
- pages
- 11431 - 11435
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000260675700016
- scopus:57149111737
- pmid:18928264
- ISSN
- 1520-5215
- DOI
- 10.1021/jp803213j
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 3cb8ac97-c19b-4e62-9801-35835f058b49 (old id 1283090)
- date added to LUP
- 2016-04-01 13:44:33
- date last changed
- 2023-04-06 11:35:11
@article{3cb8ac97-c19b-4e62-9801-35835f058b49, abstract = {{New basis sets of the atomic natural orbital (ANO) type have been developed for the lanthanide atoms La-Lu. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies and some excitation energies. Computed ionization energies have an accuracy better than 0.1 eV in most cases. Two molecular applications are inluded as illustration: the cerium diatom and the LuF3 molecule. In both cases it is shown that 4f orbitals are not involved in the chemical bond in contrast to an earlier claim for the latter molecule.}}, author = {{Roos, Björn and Lindh, Roland and Malmqvist, Per-Åke and Veryazov, Valera and Widmark, Per-Olof and Borin, Antonio Carlos}}, issn = {{1520-5215}}, language = {{eng}}, number = {{45}}, pages = {{11431--11435}}, publisher = {{The American Chemical Society (ACS)}}, series = {{The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory}}, title = {{New Relativistic Atomic Natural Orbital Basis Sets for Lanthanide Atoms with Applications to the Ce Diatom and LuF3}}, url = {{http://dx.doi.org/10.1021/jp803213j}}, doi = {{10.1021/jp803213j}}, volume = {{112}}, year = {{2008}}, }