On the electronic structure of Li{sub 2} (X{sup 1}{Sigma}{sub g}{sup +}) and its changes with internuclear distance

Journal Article · Tue Jun 20 04:00:00 EDT 2000 · International Journal of Quantum Chemistry

DOI:https://doi.org/10.1002/(SICI)1097-461X(2000)78:5<378::AID-QUA7>3.0.CO;2-Y· OSTI ID:20067704

Penotti, F E

A compact, yet accurate, and strictly virial-compliant ab initio electronic wavefunction for ground-state Li{sub 2} is exploited for a study of the molecule's electronic structure and electron density. Symmetry-breaking problems that emerge at the single-configuration level are solved in a multiconfigurational spin-coupled approach that enables simultaneous optimization of angularly correlated resonating configurations. Particular emphasis is placed on the accurate determination of the electron density's bifurcation points and of the quadrupole moment as a function of internuclear distance R. Tentative connections are drawn between the R dependence of the electron density's topological structure and quadrupole moment and that of the electronic wavefunction. Computation of the latter constitutes the first application to systems other than isolated atoms of the optimized basis set generalized multiconfiguration spin-coupled method, which entails use of nonorthogonal orbitals and Slater-type functions with variationally optimized exponential parameters.

• Research Organization: CNR, CSRSRC, Milan (IT)
• OSTI ID: 20067704
• Journal Information: International Journal of Quantum Chemistry, Journal Name: International Journal of Quantum Chemistry Journal Issue: 5 Vol. 78; ISSN IJQCB2; ISSN 0020-7608
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
ELECTRONIC STRUCTURE
GROUND STATES
LITHIUM
MOLECULES
QUADRUPOLE MOMENTS
SLATER METHOD
WAVE FUNCTIONS