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The vibrational frequencies of ozone

J. Chem. Phys. 93, 489 (1990); doi:10.1063/1.459548

Issue Date: 1 July 1990

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Timothy J. Lee
NASA Ames Research Center, Moffett Field, California 94035

Gustavo E. Scuseria
Department of Chemistry and Rice Quantum Institute, Rice University, Houston, Texas 77251
The equilibrium structure and harmonic frequencies of ozone have been determined at various levels of coupled-cluster theory using large one-particle basis sets. We have used the singles and doubles coupled-cluster (CCSD) method, the recently proposed CCSD(T) method, and the CCSDT-1 method. The largest one-particle basis sets utilize the atomic natural orbital (ANO) general contraction scheme and contain up through g-type functions. It is shown that f-type functions are essential for obtaining quantitative accuracy in the equilibrium structure and the harmonic frequencies (i.e.,±0.003 Å and ± 30 cm−1). The CCSD(T) level of theory in conjunction with a [4s 3p 2d 1f] ANO basis set is found to yield an equilibrium geometry and harmonic frequencies in excellent agreement with experiment. At this level of theory the harmonic frequencies are omega1(a1)=1152, omega2(a)1=717, and omega3(b2)=1057 cm−1 to be compared with the experimental values of 1135, 716, and 1089 cm−1, respectively. This success encouraged us to determine the cubic and quartic force constants and evaluate the anharmonic corrections to the fundamental vibrational frequencies. This level of theory is shown to be quite good for the a1 vibrational modes, but some of the cubic force constants involving omega3(b2) are shown to have large errors leading to an anharmonic correction for the asymmetric stretch that is about a factor of 2 too large. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 24 January 1990; accepted 28 March 1990
Permalink: http://link.aip.org/link/?JCPSA6/93/489/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.10.Gx
    Molecular spectra and interactions of molecules with photons Calculation of molecular spectra Vibrational analysis
  • 35.20.Pa
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Rotation, vibration, and vibrationrotation constants
  • YEAR: 1990

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (35)
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