Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on first row diatomic hydrides

Journal Article · Sun Aug 01 04:00:00 EDT 1993 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.465307· OSTI ID:6235282

Peterson, K A; Kendall, R A; Dunning, Jr, T H ^[1]

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1. Molecular Science Research Center, Pacific Northwest Laboratory Richland, Washington 99352 (United States)

Potential energy functions have been calculated for the electronic ground states of the first row diatomic hydrides BH, CH, NH, OH, and HF using single- (HF+1+2) and multi- (GVB+1+2 and CAS+1+2) reference internally contracted single and double excitation configuration interaction (CI) wave functions. The convergence of the derived spectroscopic constants and dissociation energies with respect to systematic increases in the size of the one-particle basis set has been investigated for each method using the correlation consistent basis sets of Dunning and co-workers. The effect of augmenting the basis sets with extra diffuse functions has also been addressed. Using sets of double (cc-pVDZ) through quintuple (cc-pV5Z) zeta quality, the complete basis set (CBS) limits for [ital E][sub [ital e]], [ital D][sub [ital e]], [ital r][sub [ital e]], and [omega][sub [ital e]] have been estimated for each theoretical method by taking advantage of the regular convergence behavior. The estimated CBS limits are compared to the available experimental results, and the intrinsic errors associated with each theoretical method are discussed. The potential energy functions obtained from GVB+1+2 and CAS+1+2 calculations are observed to yield very comparable spectroscopic constants, with errors in [ital D][sub [ital e]] ranging from 0.4 kcal/mol for BH to 2.9 kcal/mol for HF. The contraction errors associated with the internally contracted multireference CI have also been calculated for each species; while found to increase from BH to HF, they are, in general, small for all calculated spectroscopic constants. For the cc-pVDZ basis sets, spectroscopic constants have also been determined from full CI calculations.

• DOE Contract Number: AC06-76RL01830; FG06-89ER75522
• OSTI ID: 6235282
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 99:3; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

664100* -- Theory of Electronic Structure of Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
BORON COMPOUNDS
BORON HYDRIDES
CARBON
CARBYNES
CONFIGURATION INTERACTION
CORRELATIONS
ELECTRON CORRELATION
ELEMENTS
ENERGY
ENERGY LEVELS
EXCITED STATES
FLUORINE COMPOUNDS
FUNCTIONS
GROUND STATES
HALOGEN COMPOUNDS
HYDRIDES
HYDROFLUORIC ACID
HYDROGEN COMPOUNDS
HYDROXYL RADICALS
INORGANIC ACIDS
MOLECULES
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NONMETALS
POTENTIAL ENERGY
RADICALS
ROTATIONAL STATES
VIBRATIONAL STATES
WAVE FUNCTIONS