Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for second-row elements

Journal of Chemical Physics - Tập 77 Số 7 - Trang 3654-3665 - 1982
Michelle Francl1, William J. Pietro1, Warren J. Hehre1, J. Stephen Binkley2, Mark S. Gordon3, D. J. Defrees4, John A. Pople4
1Department of Chemistry, University of California, Irvine, California, 92717
2Theoretical Division, Sandia Laboratory, Livermore, California 94550
3Department of Chemistry, North Dakota State University, Fargo, North Dakota 58102
4Department of Chemistry, Carnegie-Mellon University, Pittsburgh, Pennsylvania 15213.

Tóm tắt

The 6-31G* and 6-31G** basis sets previously introduced for first-row atoms have been extended through the second-row of the periodic table. Equilibrium geometries for one-heavy-atom hydrides calculated for the two-basis sets and using Hartree–Fock wave functions are in good agreement both with each other and with the experimental data. HF/6-31G* structures, obtained for two-heavy-atom hydrides and for a variety of hypervalent second-row molecules, are also in excellent accord with experimental equilibrium geometries. No large deviations between calculated and experimental single bond lengths have been noted, in contrast to previous work on analogous first-row compounds, where limiting Hartree–Fock distances were in error by up to a tenth of an angstrom. Equilibrium geometries calculated at the HF/6-31G level are consistently in better agreement with the experimental data than are those previously obtained using the simple split-valance 3-21G basis set for both normal- and hypervalent compounds. Normal-mode vibrational frequencies derived from 6-31G* level calculations are consistently larger than the corresponding experimental values, typically by 10%–15%; they are of much more uniform quality than those obtained from the 3-21G basis set. Hydrogenation energies calculated for normal- and hypervalent compounds are in moderate accord with experimental data, although in some instances large errors appear. Calculated energies relating to the stabilities of single and multiple bonds are in much better accord with the experimental energy differences.

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Tài liệu tham khảo

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Thông tin
Thông tin xuất bản

Journal of Chemical Physics

Tập 77 Số 7

3654-3665

Thông tin tác giả