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Explanation of Some Differences in the Correlation Energies of CH_4, Ne, and NH_4^+

McKoy, Vincent (1965) Explanation of Some Differences in the Correlation Energies of CH_4, Ne, and NH_4^+. Journal of Chemical Physics, 42 (6). pp. 2232-2325. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20151028-114743668

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Abstract

The most recent nonempirical value for the correlation energy of CH_4, E_(corr)(CH_4), is −0.344 a.u. Prior to this, E_(corr) of the isoelectronic systems Ne and CH_4 had been assumed equal (−0.393 a.u.). This paper gives a simple explanation of 50% of this difference, that is, from electrostatics the four protons in CH_4 smeared over a sphere (spherical model) and only six at the center exert a smaller potential than all 10 at the center do in neon. This leads to a much larger effective nuclear charge for the orbitals in Ne. The Z dependence of E(corr) of Ne‐like ions then sets |E_(corr)(CH_4)| at 0.025 a.u. less than |E_(corr)(Ne)|. This approach will be useful in relating molecular E_(corr)'s to the correlation energy of related and better‐understood atomic systems and in locating molecular Hartree—Fock limits. Two other results in this paper are (a) E_(corr)(NH_4^+) given as −0.330 a.u. is too low and should be at least 0.344 a.u., that is, E_(corr)(CH_4). This suggests a better choice for the proton affinity of NH_3. (b) |E_(corr)(SiH_4)| will be about 0.08 a.u. less than |E_(corr)(argon)|.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1696272DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/42/6/10.1063/1.1696272PublisherArticle
Alternate Title:Explanation of Some Differences in the Correlation Energies of CH4, Ne, and NH4+
Additional Information:© 1965 American Institute of Physics. (Received 29 October 1964)
Issue or Number:6
Record Number:CaltechAUTHORS:20151028-114743668
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151028-114743668
Official Citation:Explanation of Some Differences in the Correlation Energies of CH4, Ne, and NH4+ McKoy, Vincent, The Journal of Chemical Physics, 42, 2232-2235 (1965), DOI:http://dx.doi.org/10.1063/1.1696272
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61689
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:28 Oct 2015 20:31
Last Modified:03 Oct 2019 09:10

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