Abstract
Full CI calculations of first- and second-order properties are presented to provide benchmark results for comparisons with other methods, such as multireference CI(MRCI). The full CI(FCI) polarizability of F− is computed using a double zeta plus polarization plus diffuse basis set. These FCI results are compared to those obtained at other levels of theory; the CASSCF/MRCI with Davidson correction results are in excellent agreement with the FCI. Differences between the polarizability results computed as a (numerical) second derivative of the energy or as an induced dipole moment are also discussed. FCI calculations are presented for the dipole moment and polarizability of HF, CH2 and SiH2 using a DZP basis set. Again, the CASSCF/MRCI values are in excellent agreement with the FCI results, whereas SDCI values, whether computed as an expectation value or as an energy derivative, are much worse. The results obtained using the CPF approach are in considerably better agreement with the FCI results than SDCI, and are similar in quality to the SDCI energy derivative results with the inclusion of Davidson's correction.
Similar content being viewed by others
References
Saxe P, Schaefer HF, Handy NC (1981) Chem Phys Lett 79:202
Harrison RJ, Handy NC (1983) Chem Phys Lett 96:386
Siegbahn PEM (1984) Chem Phys Lett 109:417
Knowles PJ, Handy NC (1984) Chem Phys Lett 111:315
Bauschlicher CW, Langhoff SR, Taylor PR, Handy NC, Knowles PJ (1986) J Chem Phys 85:1469
Bauschlicher CW, Taylor PR (1986) J Chem Phys 85:6510
Bauschlicher CW, Taylor PR (1987) J Chem Phys 86:1420
Bauschlicher CW, Langhoff SR, Partridge H, Taylor PR (1986) J Chem Phys 85:3407
Bauschlicher CW, Taylor PR (1986) J Chem Phys 85:2779
Bauschlicher CW, Taylor PR (1987) J Chem Phys 86:858
Dunning TH (1970) J Chem Phys 53:2823; Huzinaga S (1965) J Chem Phys 42:1293
Dunning TH, Hay PJ (1977). In: Schaefer HF (ed) Methods of electronic structure theory. Plenum Press, New York, pp 1–27
Ahlrichs R, Driessler F, Lischka H, Staemmler V (1975) J Chem Phys 62:1235
Ahlrichs R, Scharf P, Ehrhardt C (1985) J Chem Phys 82:890
Bunge A (1970) J Chem Phys 53:20; McLean AD, Liu B (1973) J Chem Phys 58:1066; Bender CF, Schaefer HF (1971) J Chem Phys 55:7498
Siegbahn PEM, Heiberg A, Roos BO, Levy B (1980) Physica Scripta 21:323; Roos BO, Taylor PR, Siegbahn PEM (1980) Chem Phys, 48:157; Roos BO (1980) Int J Quantum Chem S14:175
Langhoff SR, Davidson ER (1974) Int J Quantum Chem 8:61
Diercksen GHF, Roos BO, Sadlej AJ (1981) Chem Phys 59:29
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Bauschlicher, C.W., Taylor, P.R. Full CI benchmark calculations for molecular properties. Theoret. Chim. Acta 71, 263–276 (1987). https://doi.org/10.1007/BF00529098
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00529098