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Issue 109, 2014
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Valence and Rydberg states of CH3Cl: a MR-CISD study

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Abstract

In this work ten singlet and nine triplet states are studied through multi-reference configuration interactions with singles and doubles (MR-CISD), including Davidson extensivity correction (MR-CISD+Q). For the first time the excited states whose energies are larger than ∼9.5 eV have been calculated using highly correlated methods. The energies, spatial extent (〈r2〉), configurations weights and oscillator strengths (f) have been computed. At the MR-CISD+Q level the excited states energies vary from ∼7.51 to 11.98 eV. The lowest (nσ*) excited singlet state is significantly mixed with the n3pa1 and n3s Rydberg states, while the next (n3s) has a non-negligible mixture with the nσ* state. The next three singlet states obtained result from the (nCl)3(3pe)1 configuration and are almost degenerate. The next (n3pa1) singlet state is significantly mixed with the nσ* state, while the last three have σC–Cl → Rydberg (3s or 3p) as the main configurations. According to the f values the most intense transition is to the 41A1 state, a σ3pa1 Rydberg state mixed with the σσ* and σ3s configurations. Our results indicate that the σσ* configuration is responsible for the high f value of the gs → 41A1 transition. The Rydberg-valence mixing is greatly reduced in the triplet states whose singlet counterparts have significant multiconfigurational character. The 23A1 state (σσ*) does not have its singlet counterpart, while the 41A1 state (σ3pa1 + σσ* + σ3s) does not have its triplet counterpart. The obtained results are in good agreement with experimental results and with previous CASPT2 results.

Graphical abstract: Valence and Rydberg states of CH3Cl: a MR-CISD study

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Article information


Submitted
16 Sep 2014
Accepted
17 Nov 2014
First published
19 Nov 2014

RSC Adv., 2014,4, 64085-64092
Article type
Paper
Author version available

Valence and Rydberg states of CH3Cl: a MR-CISD study

V. C. de Medeiros, S. A. do Monte and E. Ventura, RSC Adv., 2014, 4, 64085
DOI: 10.1039/C4RA10567B

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