2017
DOI: 10.1016/j.jms.2017.02.006
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Computing sextic centrifugal distortion constants by DFT: A benchmark analysis on halogenated compounds

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Cited by 25 publications
(9 citation statements)
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“…The computed values of the Φ JK , Φ K , ϕ JK , and ϕ K parameters show errors within 10% from the experimental counterparts, as expected on the basis of previous benchmark studies. 37 , 73 However, a discrepancy of about 60% in opposite directions is observed for Φ J and ϕ J . A possible explanation for this behavior may be rooted in the small values, especially of Φ J , that make their precise determination a difficult task.…”
Section: Resultsmentioning
confidence: 93%
“…The computed values of the Φ JK , Φ K , ϕ JK , and ϕ K parameters show errors within 10% from the experimental counterparts, as expected on the basis of previous benchmark studies. 37 , 73 However, a discrepancy of about 60% in opposite directions is observed for Φ J and ϕ J . A possible explanation for this behavior may be rooted in the small values, especially of Φ J , that make their precise determination a difficult task.…”
Section: Resultsmentioning
confidence: 93%
“…In fact, it has been shown that B2 calculations of vibrational frequencies and intensities can reach an average accuracy often within 10 cm −1 and a few km mol −1 , respectively (Biczysko et al, 2010;Puzzarini et al, 2019a;Boussessi et al, 2020a), thus performing equally to, or even better than, the CCSD(T)/cc-pVTZ approach. Concerning the prediction of rotational spectroscopic parameters, the same B2/B3 approach has been validated in several studies concerning rotational constants (Spada et al, 2017a;Li et al, 2018) together with quartic centrifugal distortion parameters (Tasinato, 2014;Boussessi et al, 2020a) and, very recently, also for sextic centrifugal distortion parameters (Pietropolli Charmet et al, 2017;Boussessi et al, 2020b). In the present work, hybrid and double-hybrid density functionals of the "last-generation" are analyzed to check if they provide improved performances with respect to the B3 and B2 paradigms.…”
Section: Introductionmentioning
confidence: 93%
“…As can be seen, the theoretical results obtained at the different levels of theory employed are in good overall agreement, with only the PW6B95 seeming to yield slightly larger values for the and centrifugal distortion parameters. Comparing the computed vales of , and with the experimental counterparts, a general good agreement can be noted, even though, according to the expected accuracy of the calculations [ 46 , 77 ], the relative deviations between 10 and 15% suggest that the rotational spectra of this molecule may deserve additional investigations, with the aim of extending the analysis toward higher rotational quantum numbers ( J in particular). This should lead to the determination of the missing sextic centrifugal distortion parameters, which, in turn, can also affect the values of the remaining ones.…”
Section: Results and Discussionmentioning
confidence: 55%
“…Both of them consider the extrapolation to the complete basis set (CBS) limit and account for core correlation effects, but the former is formally justified by exploiting the additivity rule to build the gradient used in the geometry optimization, whereas the ChS assumes that the additivity relation can be applied directly on geometrical parameters. On the basis of the available data, both methods are expected to predict bond lengths and valence angles with an accuracy within 2 mÅ and 0.1−0.2°, respectively [ 43 , 44 , 45 , 46 , 47 ]. The ChS was also used for the computation of harmonic frequencies of vibration, as well as for obtaining quartic centrifugal distortion constants and nuclear quadrupolar coupling constants due to the presence of the Cl nucleus.…”
Section: Materials and Methodsmentioning
confidence: 99%