Geometry optimizations in the zero order regular approximation for relativistic effects

Abstract

Analytical expressions are derived for the evaluation of energy gradients in the zeroth order regular approximation ͑ZORA͒ to the Dirac equation. The electrostatic shift approximation is used to avoid gauge dependence problems. Comparison is made to the quasirelativistic Pauli method, the limitations of which are highlighted. The structures and first metal-carbonyl bond dissociation energies for the transition metal complexes W͑CO͒ 6 , Os͑CO͒ 5 , and Pt͑CO͒ 4 are calculated, and basis set effects are investigated.

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

“…The CCSD(T) calculations were performed with the MOLPRO 2012 program package. [64,65] The spin-orbit calculations were performed with the ADF code [66,67] at the ZORA-spin orbit level [68][69][70][71][72] with the BLYP functional [40,73] and the TZ2P basis set. The calculations were performed on our local (UA and WSU) Opteron-based and Xeonbased Linux clusters.…”

Influence of Carbon Support on Electronic Structure and Catalytic Activity of Pt Catalysts: Binding to the CO Molecule

“…18,32,38 The relativistic effects are taken into account at the all-electron level with the zero-orderregular approximation (ZORA) approach. [39][40][41][42][43][44] The molecular orbitals (MOs) were expanded in an uncontracted set of Slater-type orbitals (STO), based on a basis set study. This computational approach has been successful to describe the Pt/C and Co/C interactions.…”

Phospha-Fischer Carbenes: Synthesis, Structure, Bonding, and Reactions of Pd(0)− and Pt(0)−Phosphenium Complexes

“…59,60 Scalar relativistic effects were taken into account in all EDA calculations by employing the ZORA Hamiltonian. [61][62][63] Representations of the molecular orbitals of 2 and 7 given in Figure 2 were constructed using the gOpenMol program. 64,65 Results …”