AnINDO/S-CI treatment including spin-orbit interaction based on Rumer spin functions. Application to the hydrated cerium ion

Abstract

We examine the inclusion of spin-orbit effects within the Rumer configuration interaction technique and discuss its implementation in the spectroscopic version of the intermediate neglect of differential overlap model ( INDO/S-CI). An efficient strategy for calculating excitation energies, transition moments, and Mulliken populations for Rumer-adapted functions is described. As an example, results are presented for the ground and excited states of the hydrated trivalent cerium ion [Ce( H20)9]3f, which confirm the low energy assignments to 4f+ 5d transitions split by some 10000 cm-' through spin-orbit coupling and ligand field interaction. Comparisons are made between this technique and one that we have used previously that utilizes configuration interaction over double-group adapted linear combinations of determinants.

Absorption, Fluorescence, and Magnetic Circular Dichroism Spectra of and Molecular Orbital Calculations on Tetrabenzotriazaporphyrins and Tetranaphthotriazaporphyrins

“…The structures were refined using a modified MM2 force field calculation in the Mechanics program of the CAChe system . The structures were optimized at the restricted Hartree−Fock self-consistent field (SCF) level in the case of the diamagnetic species and at the restricted open-shell Hartree−Fock (ROHF) SCF level in the case of the paramagnetic species using the ZINDO program in the CAChe software package . These SCF optimizations were carried out at the intermediate neglect of differential overlap/1 (INDO/1) level of approximation.…”

Assignment of the optical spectrum of metal porphyrin and phthalocyanine radical anions

“…The structure was refined using a modified MM2 force field calculation in the Mechanics program of the CAChe system [40]. The structures of ZnTPP(À2) and the [ZnTPP(À3)] À species were optimized at the restricted Hartree-Fock self-consistent field (SCF) level [41] in the case of ZnTPP(À2) and at the restricted open-shell HartreeFock (ROHF) SCF level [42][43][44][45][46][47] in the case of [ZnTPP(À3)] À using the ZINDO program in the CAChe software package [48][49][50][51][52][53][54][55][56][57]. These SCF optimizations were carried out at the intermediate neglect of differential overlap/1 (INDO/1) [58] level of approximation.…”

On the agostic interaction in lanthanide phenylene complexes: An INDO study of [(CpM)2C6H4] (M = Sc, Lu) employing an energy‐partitioning analysis

“…The two-center two-electron integrals are calculated from Slater-Condon integrals Fo(pp) using the Mataga-Nishimoto approximation [6,19,41]. The spectroscopic INDO model has been extended successfully to the lanthanide elements [12,13]. The values for the integrals Fo(pv) were derived from atomic spectra, supplemented by numerical Dirac-Fock calculations.…”

“…The corresponding spectroscopic modification INDO/S has so far been successfully applied to organic molecules [19] and to a variety of transition-metal compounds [6,20]. The INDO/S-CI method has been augmented recently by a treatment of the spin-orbit interaction [13,21]. This extension allowed the successful calculation of excited-state properties of compounds that contain heavy elements, such as the lanthanides [12,13,20-231.…”