Erratum: <i>Ab initio</i> relativistic effective potentials with spin–orbit operators. IV. Cs through Rn [J. Chem. Phys. <b>93</b>, 6654 (1990)]

Ross, Ronald J.; Powers, Joseph M.; Atashroo, T.; Ermler, Walter C.; LaJohn, L.A.; Christiansen, P. A.

doi:10.1063/1.468517

Cited by 91 publications

(113 citation statements)

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“…10͒ of Cs by the spin-averaged shape-consistent relativistic pseudopotential. 19 Atomic Gaussian basis sets ͓͑15s10p5d3f͒ / ͓8s6p5d3f͔ with contracted inner functions for Na and uncontracted ͑8s7p6d3f͒ for Cs͔ were obtained by appropriate extension of the basis from Refs. 19 and 20, respectively ͑see also Ref.…”

Section: A Outline Of Methodsmentioning

confidence: 99%

Experimental and theoretical studies of Λ doublings and permanent electric dipoles in the low-lying Π1 states of NaCs

Zaharova

Nikolayeva

Tamanis

et al. 2006

The Journal of Chemical Physics

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We present experimental data on the electric permanent dipole moments d(v',J') and lambda splittings (q factors) in the quasidegenerate (3) 1pi(e/f) state of the NaCs molecule over a wide range of the vibrational (v') and rotational (J') quantum numbers by using the combination of dc Stark mixing and electric radio frequency-optical double resonance methods. Within the experimental (3) 1pi state v' ranged from v' = 0 to 34, q values exhibited a pronounced decrease from 7.91x10(-6) to 0.47x10(-6) cm(-1), while absolute value(d) values varied between 8.0 and 5.0 D. Experimental evaluation yielded small d values about 1 D for D2 1pi state v' < 3 levels. The experiment is supported by ab initio electronic structure calculations performed for the (1-3) 1pi states of NaCs by means of the many-body multipartitioning perturbation theory of potential energy curves, permanent dipole, and angular coupling matrix elements for the lowest singlet states. The predicted d values reproduce their experimental counterparts within the measurement errors while theoretical q factors reproduce the measured v' dependence being, however, systematically overestimated by ca. 1x10(-6) cm(-1). The present NaCs data are compared with those of the NaK and NaRb molecules.

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Section: A Outline Of Methodsmentioning

confidence: 99%

Experimental and theoretical studies of Λ doublings and permanent electric dipoles in the low-lying Π1 states of NaCs

Zaharova

Nikolayeva

Tamanis

et al. 2006

The Journal of Chemical Physics

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“…2.1. Static calculations with Gaussian 98 :32 DZVP and TZVP basis sets of Godbout et al33 were used for the elements H, C, O, F and P, while Rh was described by the small‐core quasirelativistic effective core potential of Christiansen et al and a double‐zeta valence basis (abbreviated CE) 34.…”

Section: Methods Of Calculationmentioning

confidence: 99%

Computational Approaches to Activity in Rhodium‐Catalysed Hydroformylation

Gleich

Hutter

2004

Chemistry A European J

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In this theoretical study on rhodium-catalysed hydroformylation we examine an unmodified hydridorhodium(I) carbonyl system a together with three variants modified by the model phosphane ligands PF3 (system b), PH3 (system c) and PMe3 (system d), which show increasing basicity on the Tolman chi parameter scale. The olefinic substrate for all systems is ethene. Based on the dissociative hydroformylation mechanism, static and dynamic quantum-mechanical approaches are made for preequilibria and the whole catalytic cycle. Agreement with experimental results was achieved with regard to the predominance of phosphane monocoordination in systems b-d, different sensitivity of unmodified and modified systems towards hydrogen pressure and the early location of the rate-determining step. Neither the catalytic cycle as a whole nor olefin insertion as an important selectivity-determining step gives a clear picture of activity differences among a-d. However, the crucial first catalytic step, association of ethene to the active species [HRhL3] (L=CO, PR3), may play the key role in the experimentally observed higher activity of a and systems with less basic phosphane ligands modelled by b.

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“…21 A synopsis of all basis contraction schemes, numbers of explicit valence electrons, and the exponents of the added polarization functions is given in Table 1. [33][34][35][36][37][38][39][40][41][42][43] In all the computations, the corresponding RECP and valence basis set have been considered for the iodine atoms, while lighter atoms (H, C, N, O) have been described by the 6-31G(d,p) or the 6-311ϩG(2d,2p) basis sets. 44 Two different schemes were used to describe the exchange and correlation contributions in the DFT computations.…”

Section: Computational Detailsmentioning

confidence: 99%

Comparative studies of quasi‐relativistic density functional methods for the description of lanthanide and actinide complexes

2003

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We present a comparative Density Functional Theory (DFT) study based on two different implementations of relativistic effects within the Kohn-Sham (KS) approach, to describe the metal-ligand interaction in I(3)M-L complexes (L = NH(3), NCCH(3), CO and M = La, Nd, U). In the first model, the scalar corrections were included by a quasi-relativistic approach (QR) via the so-called ZORA or Pauli Hamiltonians, while in the second, these effects are taken into account in a quasi-Relativistic Effective Core Potential (RECP). These relativistic approaches were used in conjunction with various gradient corrected (GGA) or hybrid (SCH) functionals. The structural parameters obtained from geometry optimizations have been compared to experimental structural trends, and rationalized by a KS orbital analysis. Both approaches provide similar results for mainly ionic metal-ligand bonds (e.g., for the sigma-donor ligand L = NH(3)). For the pi-acceptor ligands (NCCH(3), CO), the QR approach is in agreement with experimental trends and consistent with the presence of a backbonding interaction between U(III) and the neutral ligand, which does not exist in the lanthanide homologues. The GGA/RECP methods also reproduce this phenomenon, while the SCH/RECP scheme fails to describe this interaction. The role of the RECP, of its size, and of additional polarization functions has also been examined. Finally, the failure of the SCH/RECP approach was interpreted as a consequence of a bad estimation of frontier orbital energy levels in the uranium and ligand species.

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Erratum: Ab initio relativistic effective potentials with spin–orbit operators. IV. Cs through Rn [J. Chem. Phys. 93, 6654 (1990)]

Abstract: Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and

Cited by 91 publications

References 0 publications

Experimental and theoretical studies of Λ doublings and permanent electric dipoles in the low-lying Π1 states of NaCs

Experimental and theoretical studies of Λ doublings and permanent electric dipoles in the low-lying Π1 states of NaCs

Computational Approaches to Activity in Rhodium‐Catalysed Hydroformylation

Comparative studies of quasi‐relativistic density functional methods for the description of lanthanide and actinide complexes

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