Theoretical investigations of spectroscopic parameters and molecular constants for electronic ground state of Cl2 and its isotopes

doi:10.1088/1674-1056/19/10/103401

Abstract The potential energy curve of the Cl₂(X¹Σ_g⁺) is investigated by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in combination with the largest correlation-consistent basis set, aug-cc-pV6Z, in the valence range. The theoretical spectroscopic parameters and the molecular constants of three isotopes, ³⁵Cl₂, ³⁵Cl³⁷Cl and ³⁷Cl₂, are studied. For the ³⁵Cl₂(X¹Σ_g⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, $\alpha$_e and B_e are obtained to be 2.3921 eV, 2.4264 eV, 0.19939 nm, 555.13 cm^-1, 2.6772 cm^-1, 0.001481 cm^-1 and 0.24225 cm^-1, respectively. For the ³⁵Cl³⁷Cl(X¹Σ_g⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, $\alpha$_e and B_e are calculated to be 2.3918 eV, 2.4257 eV, 0.19939 nm, 547.68 cm^-1, 2.6234 cm^-1, 0.00140 cm¹ and 0.23572 cm^-1, respectively. And for the ³⁷Cl₂(X¹Σ_g⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, $\alpha$_e and B_e are obtained to be 2.3923 eV, 2.4257 eV, 0.19939 nm, 540.06 cm^-1, 2.5556 cm^-1, 0.00139 cm^-1 and 0.22919 cm^-1, respectively. These spectroscopic results are in good agreement with the available experimental data. With the potential of Cl₂ molecule determined at the MRCI/aug-cc-pV6Z level of theory, the total of 59 vibrational states is predicted for each isotope when the rotational quantum number J equals zero (J = 0). The theoretical vibrational levels, classical turning points, inertial rotation and centrifugal distortion constants are determined when J = 0, which are in excellent accordance with the available experimental findings.

Keywords: isotope effect spectroscopic parameter molecular constant vibrational level

Received: 01 February 2010
Revised: 20 April 2010
Accepted manuscript online:

PACS:	31.50.Bc	(Potential energy surfaces for ground electronic states)
	33.15.Mt	(Rotation, vibration, and vibration-rotation constants)
	33.20.Sn	(Rotational analysis)

Fund: Project supported by the National Natural Science Foundation of China (Grant Nos. 10874064 and 60777012), the Program for Science and Technology Innovation Talents in Universities of Henan Province of China (Grant No. 2008HASTIT008) and the Natural Science Foundation of Educational Bureau of Henan Province of China (Grant No. 2010B140013).

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Shi De-Heng(施德恒), Zhang Xiao-Niu(张小妞), Liu Hui(刘慧), Zhu Zun-Lue(朱遵略), and Sun Jin-Feng(孙金锋) Theoretical investigations of spectroscopic parameters and molecular constants for electronic ground state of Cl₂ and its isotopes 2010 Chin. Phys. B 19 103401

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Theoretical investigations of spectroscopic parameters and molecular constants for electronic ground state of Cl2 and its isotopes

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Theoretical investigations of spectroscopic parameters and molecular constants for electronic ground state of Cl₂ and its isotopes