Theoretical Chemistry Accounts

, Volume 103, Issue 2, pp 141–145

TiCl, TiH, and TiH+ bond energies: a test of a correlation-consistent Ti basis set

  • Charles W. Bauschlicher Jr
Regular article

DOI: 10.1007/s002140050524

Cite this article as:
Bauschlicher Jr, C. Theor Chem Acc (1999) 103: 141. doi:10.1007/s002140050524

Abstract.

Correlation-consistent basis sets are developed for the Ti atom. The polarization functions are optimized for the average of the 3F and 5F states. One series of correlation-consistent basis sets is for 3d and 4s correlation, while the second series includes 3s and 3p correlation as well as 3d and 4s correlation. These basis sets are tested using the Ti 3F–5F separation and the dissociation energies of TiCl X4Φ, TiH X4Φ, and TiH+ X3Φ. The CCSD(T) complete basis set limit values are determined by extrapolation. The Douglas–Kroll approach is used to compute the scalar relativistic effect. Spin-orbit effects are taken from experiment and/or are computed at the CASSCF level. The Ti 3F–5F separation is in excellent agreement with experiment, while the TiCl, TiH, and TiH+ bond energies are in good agreement with experiment. Extrapolation with the valence basis set is consistent with other atoms, while including 3s and 3p correlation appears to make extrapolation more difficult.

Key words: Basis SetBond energiesCorrelation-consistentInner-shell correlation

Copyright information

© Springer-Verlag Berlin Heidelberg 1999

Authors and Affiliations

  • Charles W. Bauschlicher Jr
    • 1
  1. 1.Mail Stop 230-3, NASA Ames Research Center, Moffett Field, CA 94035, USAUS