Development and testing of a compact basis set for use in effective core potential calculations on rhodium complexes

• Published in: Journal of computational chemistry Vol. 33; no. 26; pp. 2049 - 2057
• Main Authors: Roscioni, Otello M., Lee, Edmond P. F., Dyke, John M.
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 05-10-2012; Wiley Subscription Services, Inc
• Subjects: Analytical chemistry; basis set; catalysis; ECP; Electrocatalysis; Electrons; Molecular Structure; Organometallic Compounds - chemistry; Physical properties; Quantum Theory; rhodium; Rhodium - chemistry; Simulation; Thermodynamics
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.23034

We present a set of effective core potential (ECP) basis sets for rhodium atoms which are of reasonable size for use in electronic structure calculations. In these ECP basis sets, the Los Alamos ECP is used to simulate the effect of the core electrons while an optimized set of Gaussian functions, which includes polarization and diffuse functions, is used to describe the valence electrons. These basis sets were optimized to reproduce the ionization energy and electron affinity of atomic rhodium. They were also tested by computing the electronic ground state geometry and harmonic frequencies of [Rh(CO)2μ‐Cl]2, Rh(CO)2ClPy, and RhCO (neutral and its positive, and negative ions) as well as the enthalpy of the reaction of [Rh(CO)2μ‐Cl]2 with pyridine (Py) to give Rh(CO)2ClPy, at different levels of theory. Good agreement with experimental values was obtained. Although the number of basis functions used in our ECP basis sets is smaller than those of other ECP basis sets of comparable quality, we show that the newly developed ECP basis sets provide the flexibility and precision required to reproduce a wide range of chemical and physical properties of rhodium compounds. Therefore, we recommend the use of these compact yet accurate ECP basis sets for electronic structure calculations on molecules involving rhodium atoms. © 2012 Wiley Periodicals, Inc.
Accurate electronic structure calculations on rhodium molecules which use compact yet accurate basis sets are presented. The basis sets for rhodium atoms have been optimized to reproduce the ionization energy and electron affinity of atomic rhodium, and have been extensively tested by computing the electronic ground state geometry and harmonic frequencies of several molecules containing rhodium. Good agreement with experimental values was obtained.