Abstract
Ab initio quantum mechanical methods, including the self-consistent field (SCF), single- and double-excitation configuration interaction (CISD), single- and double-excitation coupled cluster (CCSD), and the single-, double-, and perturbative triple-excitation coupled cluster [CCSD(T)] have been applied to three stationary points on the SiH7+ potential energy hypersurface. Double-ζ plus polarization (DZP) and triple-ζ plus double-polarization [TZ2P and TZ2P(f,d)] basis sets were employed. The C2 structure, where two symmetry-equivalent H2 subunits complex the SiH3+ cation, was found to be the global minimum, in agreement with the findings of Liu and Zhou (J. Phys. Chem. 1993, 97, 9555). The bound vs free H2 harmonic vibrational frequency shift obtained at the TZ2P CCSD level (259 cm-1) is 36 cm-1 less than the experimental frequency shift (295 cm-1), compared with the shift obtained by Liu and Zhou with second-order perturbation theory, which was 33 cm-1 higher than the value from experiment. The theoretical rotational constants are compared with the experiments of Okumura's group. The dissociation energy D0 of SiH7+ to yield SiH5+ and H2 is sizable, 4.6 kcal/mol [TZ2P(f,d)] CCSD-(T) + ZPVE(TZ2P CCSD)], much larger than the analogous value for CH7+.
| Original language | English |
|---|---|
| Pages (from-to) | 5040-5043 |
| Number of pages | 4 |
| Journal | Journal of physical chemistry |
| Volume | 98 |
| Issue number | 19 |
| DOIs | |
| Publication status | Published - 1994 Jan 1 |
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All Science Journal Classification (ASJC) codes
- Engineering(all)
- Physical and Theoretical Chemistry
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Structure, infrared spectrum, and dissociation energy of SiH7+. / Hu, Ching Han; Schreiner, Peter R.; Von Ragué Schleyer, Paul; Schaefer, Henry F.
In: Journal of physical chemistry, Vol. 98, No. 19, 01.01.1994, p. 5040-5043.Research output: Contribution to journal › Article
TY - JOUR
T1 - Structure, infrared spectrum, and dissociation energy of SiH7+
AU - Hu, Ching Han
AU - Schreiner, Peter R.
AU - Von Ragué Schleyer, Paul
AU - Schaefer, Henry F.
PY - 1994/1/1
Y1 - 1994/1/1
N2 - Ab initio quantum mechanical methods, including the self-consistent field (SCF), single- and double-excitation configuration interaction (CISD), single- and double-excitation coupled cluster (CCSD), and the single-, double-, and perturbative triple-excitation coupled cluster [CCSD(T)] have been applied to three stationary points on the SiH7+ potential energy hypersurface. Double-ζ plus polarization (DZP) and triple-ζ plus double-polarization [TZ2P and TZ2P(f,d)] basis sets were employed. The C2 structure, where two symmetry-equivalent H2 subunits complex the SiH3+ cation, was found to be the global minimum, in agreement with the findings of Liu and Zhou (J. Phys. Chem. 1993, 97, 9555). The bound vs free H2 harmonic vibrational frequency shift obtained at the TZ2P CCSD level (259 cm-1) is 36 cm-1 less than the experimental frequency shift (295 cm-1), compared with the shift obtained by Liu and Zhou with second-order perturbation theory, which was 33 cm-1 higher than the value from experiment. The theoretical rotational constants are compared with the experiments of Okumura's group. The dissociation energy D0 of SiH7+ to yield SiH5+ and H2 is sizable, 4.6 kcal/mol [TZ2P(f,d)] CCSD-(T) + ZPVE(TZ2P CCSD)], much larger than the analogous value for CH7+.
AB - Ab initio quantum mechanical methods, including the self-consistent field (SCF), single- and double-excitation configuration interaction (CISD), single- and double-excitation coupled cluster (CCSD), and the single-, double-, and perturbative triple-excitation coupled cluster [CCSD(T)] have been applied to three stationary points on the SiH7+ potential energy hypersurface. Double-ζ plus polarization (DZP) and triple-ζ plus double-polarization [TZ2P and TZ2P(f,d)] basis sets were employed. The C2 structure, where two symmetry-equivalent H2 subunits complex the SiH3+ cation, was found to be the global minimum, in agreement with the findings of Liu and Zhou (J. Phys. Chem. 1993, 97, 9555). The bound vs free H2 harmonic vibrational frequency shift obtained at the TZ2P CCSD level (259 cm-1) is 36 cm-1 less than the experimental frequency shift (295 cm-1), compared with the shift obtained by Liu and Zhou with second-order perturbation theory, which was 33 cm-1 higher than the value from experiment. The theoretical rotational constants are compared with the experiments of Okumura's group. The dissociation energy D0 of SiH7+ to yield SiH5+ and H2 is sizable, 4.6 kcal/mol [TZ2P(f,d)] CCSD-(T) + ZPVE(TZ2P CCSD)], much larger than the analogous value for CH7+.
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U2 - 10.1021/j100070a015
DO - 10.1021/j100070a015
M3 - Article
AN - SCOPUS:5244370342
VL - 98
SP - 5040
EP - 5043
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 19
ER -