Pseudopotential SCF–MO studies of hypervalent compounds. I. XeF2 and XeF4
dc.contributor.author | Bartell, Lawrence S. | en_US |
dc.contributor.author | Rothman, Michael J. | en_US |
dc.contributor.author | Ewig, Carl S. | en_US |
dc.contributor.author | Van Wazer, John R. | en_US |
dc.date.accessioned | 2010-05-06T22:46:07Z | |
dc.date.available | 2010-05-06T22:46:07Z | |
dc.date.issued | 1980-07-01 | en_US |
dc.identifier.citation | Bartell, Lawrence S.; Rothman, Michael J.; Ewig, Carl S.; Van Wazer, John R. (1980). "Pseudopotential SCF–MO studies of hypervalent compounds. I. XeF2 and XeF4." The Journal of Chemical Physics 73(1): 367-374. <http://hdl.handle.net/2027.42/70823> | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/70823 | |
dc.description.abstract | The (ab initio) effective potential theory developed by Ewig et al. has been applied to a series of hypervalent compounds with a view to elucidating the anomalous properties of several of the higher fluorides of xenon and iodine. In this initial paper the development of a minimal basis set substantially better than an STO‐4G atom‐optimized set is described. Calculations carried out on XeF2 and XeF4 give valence orbital energies in fair agreement with those obtained with the more flexible, all‐electron SCF–MO calculations by Basch et al. Equilibrium structures of XeF2 and XeF4 provided by the effective potential calculations possess the correct symmetries. Bond lengths, although too long by 0.09 Å, correctly reproduce the contraction observed experimentally upon fluorination of XeF2. Calculated bending and stretch–stretch interaction force constants are in pleasing agreement with experiment, as is the stretching anharmonicity. Stretching frequencies evaluated at the experimental bond length, however, are 25% high. Overall, the ability of the present treatment to give a reasonable account of the structures and force fields of XeF2 and XeF4 justifies its application to the higher fluorides where interpretations of observations are more speculative. | en_US |
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dc.format.mimetype | text/plain | |
dc.format.mimetype | application/pdf | |
dc.publisher | The American Institute of Physics | en_US |
dc.rights | © The American Institute of Physics | en_US |
dc.title | Pseudopotential SCF–MO studies of hypervalent compounds. I. XeF2 and XeF4 | en_US |
dc.type | Article | en_US |
dc.subject.hlbsecondlevel | Physics | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 | en_US |
dc.contributor.affiliationother | Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/70823/2/JCPSA6-73-1-367-1.pdf | |
dc.identifier.doi | 10.1063/1.439882 | en_US |
dc.identifier.source | The Journal of Chemical Physics | en_US |
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dc.identifier.citedreference | Because there are more force constants than frequencies, assumptions must be made before force constants can be calculated. Yeranos (Ref. 17) and Tsao et al. (Ref. 33) used Urey‐Bradley or hybrid orbital model force fields which constrain the most significant interaction constant, that for trans interactions, to zero. Nagarajan, instead, adopted P. Torkington’s recommended constraint [J. Chem. Phys. 17, 357 (1949)] and got values for krrkrr and krr′krr′ of the magnitude of the present calculated values and the XeF2XeF2 result. Unfortunately, Nagarajan’s results are flawed becuuse of the use of an incorrect eueu bending assignment. | en_US |
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dc.owningcollname | Physics, Department of |
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