Structure, infrared spectrum, and dissociation energy of SiH7+

Ching Han Hu, Peter R. Schreiner, Paul Von Ragué Schleyer, Henry F. Schaefer

Research output: Contribution to journalArticle

14 Citations (Scopus)

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 languageEnglish
Pages (from-to)5040-5043
Number of pages4
JournalJournal of physical chemistry
Volume98
Issue number19
DOIs
Publication statusPublished - 1994 Jan 1

Fingerprint

infrared spectra
dissociation
Polarization
Infrared radiation
frequency shift
Vibrational spectra
Potential energy
excitation
Cations
Positive ions
Experiments
polarization
configuration interaction
self consistent fields
energy
perturbation theory
potential energy
harmonics
cations
shift

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Hu, C. H., Schreiner, P. R., Von Ragué Schleyer, P., & Schaefer, H. F. (1994). Structure, infrared spectrum, and dissociation energy of SiH7+. Journal of physical chemistry, 98(19), 5040-5043. https://doi.org/10.1021/j100070a015
Hu, Ching Han ; Schreiner, Peter R. ; Von Ragué Schleyer, Paul ; Schaefer, Henry F. / Structure, infrared spectrum, and dissociation energy of SiH7+. In: Journal of physical chemistry. 1994 ; Vol. 98, No. 19. pp. 5040-5043.
@article{728a4374d37c4ea788256598a323e057,
title = "Structure, infrared spectrum, and dissociation energy of SiH7+",
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+.",
author = "Hu, {Ching Han} and Schreiner, {Peter R.} and {Von Ragu{\'e} Schleyer}, Paul and Schaefer, {Henry F.}",
year = "1994",
month = "1",
day = "1",
doi = "10.1021/j100070a015",
language = "English",
volume = "98",
pages = "5040--5043",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "19",

}

Hu, CH, Schreiner, PR, Von Ragué Schleyer, P & Schaefer, HF 1994, 'Structure, infrared spectrum, and dissociation energy of SiH7+', Journal of physical chemistry, vol. 98, no. 19, pp. 5040-5043. https://doi.org/10.1021/j100070a015

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 journalArticle

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+.

UR - http://www.scopus.com/inward/record.url?scp=5244370342&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=5244370342&partnerID=8YFLogxK

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 -