Chlorine nuclear quadrupole coupling in chlorodifluoroacetyl chloride: Theory and experiment

Grubbs, Garry S.; Dewberry, Christopher T.; King, Amanda E.; Lin, Wei; Bailey, William C.; Cooke, Stephen A.

doi:10.1016/j.jms.2010.07.001

Cited by 7 publications

(3 citation statements)

References 26 publications

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“…The respective Qeff values derived from the slopes are 81.568(91) mb and 64.292(86) mb, respectively.The second method has eQ/h calculated directly from the values of Q = 81.65(80) mb and 64.35(64) mb for the35 Cl and37 Cl nucleus, respectively, given by Pyykkö and Li[47], yielding the respective conversion factors of 19.185 MHz/a.u. and 15.120 MHz/a.u [36,48]…”

mentioning

confidence: 98%

Internal rotation and chlorine nuclear quadrupole coupling in 2-chloro-4-fluorotoluene explored by microwave spectroscopy and quantum chemistry

Nair

Herbers

Bailey

et al. 2021

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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2-Chloro-4-fluorotoluene was investigated using a combination of molecular jet Fourier transform microwave spectroscopy in the frequency range from 5 to 21 GHz and quantum chemistry. The molecule experiences an internal rotation of the methyl group, which causes a fine splitting of all rotational transitions into doublets with separation on the order of a few tens of kHz. In addition, hyperfine effects originating from the chlorine nuclear quadrupole moment coupling its spin to the end-over-end rotation of the molecule are observed. The torsional barrier was derived using both the rho and the combined-axis-method, giving a value of 462.5(41) cm -1 . Accurate rotational constants and quadrupole coupling constants were determined for two 35 Cl and 37 Cl isotopologues and compared with Bailey's semi-experimental quantum chemical predictions. The gas phase molecular structure was deduced from the experimental rotational constants supplemented with those calculated by quantum chemistry at various levels of theory. The values of the methyl torsional barrier and chlorine nuclear quadrupole coupling constants were compared with the theoretical predictions and with those of other chlorotoluene derivatives.

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mentioning

confidence: 98%

Internal rotation and chlorine nuclear quadrupole coupling in 2-chloro-4-fluorotoluene explored by microwave spectroscopy and quantum chemistry

Nair

Herbers

Bailey

et al. 2021

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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show abstract

“…c From the MP2/6-311++G(d,p) structure, see text. Table 6 Principal components of the 35 Cl nuclear quadrupole coupling tensor for methyl chlorodifluoroacetate, gauche-chlorodifluoro acetyl chloride [23], and chloroacetic acid [53]. g c À0.11 (13) 0.07(9) 0.012 (13) a During the diagonalization procedure the signs of v ab , v ac and v bc were chosen to follow the calculated values given in Table 1.…”

Section: Discussionmentioning

confidence: 99%

“…Lastly, chlorine nuclear electric quadrupole coupling tensors were calculated on the MP2/6-311++G(d,p) lowest energy structure. The method used is described in detail elsewhere [22,23]. Briefly, electric field gradients were calculated at B1LYP/TZV(3df,2p) level of theory, and converted to quadrupole coupling constants by factors of À19.185 and À15.120 MHz/a.u.…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%