Study of low-lying electronic states of ozone by multireference Møller-Plesset perturbation method

T. Tsuneda, H. Nakano, K. Hirao

Research output: Contribution to journalArticle

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Abstract

The geometry and relative energy of the seven low-lying electronic states of ozone and the ground state of ozonide anion have been determined in C 2v symmetry by the complete active space self-consistent field (CASSCF) and the multireference Møller-Plesset perturbation (MRMP) methods. The results are compared with the photodetachment spectra of O 3- observed recently by Arnold et al. The theoretical electron affinity of ozone is 1.965 eV, which is 0.14 eV below the experimental result of 2.103 eV. The calculated adiabatic excitation energies (assignment of Arnold et al. in parentheses) of ozone are 3A2 0.90 eV (1.18 eV), 3B2, 1.19 eV (1.30 eV), 3B 1, 1.18 eV (1.45 eV), 1A2, 1.15 eV (∼1.6 eV), 1B1, 1.65 eV (2.05 eV), and 1B 2, 3.77 eV (3.41 eV), respectively. Overall the present theory supports the assignment of Arnold et al. However, the simple considerations of geometry and energy are insufficient to determine a specific assignment of the 3B2 and 3B1 states. The dissociation energy of the ground state of ozone is computed to be 0.834 eV at the present level of theory. The present theory also predicts that none of the excited states lies below the ground state dissociation limit of O3.

Original languageEnglish
Pages (from-to)6520-6528
Number of pages9
JournalThe Journal of Chemical Physics
Volume103
Issue number15
DOIs
Publication statusPublished - Jan 1 1995

Fingerprint

Ozone
Electronic states
ozone
Ground state
perturbation
electronics
ground state
ozonides
dissociation
Electron affinity
Geometry
photodetachment
energy
Excitation energy
geometry
electron affinity
Excited states
excitation
Anions
self consistent fields

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Study of low-lying electronic states of ozone by multireference Møller-Plesset perturbation method. / Tsuneda, T.; Nakano, H.; Hirao, K.

In: The Journal of Chemical Physics, Vol. 103, No. 15, 01.01.1995, p. 6520-6528.

Research output: Contribution to journalArticle

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N2 - The geometry and relative energy of the seven low-lying electronic states of ozone and the ground state of ozonide anion have been determined in C 2v symmetry by the complete active space self-consistent field (CASSCF) and the multireference Møller-Plesset perturbation (MRMP) methods. The results are compared with the photodetachment spectra of O 3- observed recently by Arnold et al. The theoretical electron affinity of ozone is 1.965 eV, which is 0.14 eV below the experimental result of 2.103 eV. The calculated adiabatic excitation energies (assignment of Arnold et al. in parentheses) of ozone are 3A2 0.90 eV (1.18 eV), 3B2, 1.19 eV (1.30 eV), 3B 1, 1.18 eV (1.45 eV), 1A2, 1.15 eV (∼1.6 eV), 1B1, 1.65 eV (2.05 eV), and 1B 2, 3.77 eV (3.41 eV), respectively. Overall the present theory supports the assignment of Arnold et al. However, the simple considerations of geometry and energy are insufficient to determine a specific assignment of the 3B2 and 3B1 states. The dissociation energy of the ground state of ozone is computed to be 0.834 eV at the present level of theory. The present theory also predicts that none of the excited states lies below the ground state dissociation limit of O3.

AB - The geometry and relative energy of the seven low-lying electronic states of ozone and the ground state of ozonide anion have been determined in C 2v symmetry by the complete active space self-consistent field (CASSCF) and the multireference Møller-Plesset perturbation (MRMP) methods. The results are compared with the photodetachment spectra of O 3- observed recently by Arnold et al. The theoretical electron affinity of ozone is 1.965 eV, which is 0.14 eV below the experimental result of 2.103 eV. The calculated adiabatic excitation energies (assignment of Arnold et al. in parentheses) of ozone are 3A2 0.90 eV (1.18 eV), 3B2, 1.19 eV (1.30 eV), 3B 1, 1.18 eV (1.45 eV), 1A2, 1.15 eV (∼1.6 eV), 1B1, 1.65 eV (2.05 eV), and 1B 2, 3.77 eV (3.41 eV), respectively. Overall the present theory supports the assignment of Arnold et al. However, the simple considerations of geometry and energy are insufficient to determine a specific assignment of the 3B2 and 3B1 states. The dissociation energy of the ground state of ozone is computed to be 0.834 eV at the present level of theory. The present theory also predicts that none of the excited states lies below the ground state dissociation limit of O3.

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