{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T19:28:30Z","timestamp":1760297310391},"reference-count":45,"publisher":"Wiley","issue":"3","license":[{"start":{"date-parts":[[2004,9,7]],"date-time":"2004-09-07T00:00:00Z","timestamp":1094515200000},"content-version":"vor","delay-in-days":4208,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[1993,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The nature of the tetrahedral H<jats:sub>4<\/jats:sub><jats:sup>2+<\/jats:sup> stationary point (minimum or triply degenerate saddle) depends remarkably upon the theoretical level employed. Harmonic vibrational analyses with, e.g., the 6\u201031G** (and 6\u201031 + +G**) and Dunning's [4<jats:italic>s<\/jats:italic>2<jats:italic>p<\/jats:italic>1<jats:italic>d<\/jats:italic>;2<jats:italic>s<\/jats:italic>1<jats:italic>p<\/jats:italic>] [D95(<jats:italic>d<\/jats:italic>,<jats:italic>p<\/jats:italic>)] basis sets using the standard <jats:italic>p<\/jats:italic> exponent suggest (erroneously) that the <jats:italic>T<\/jats:italic><jats:sub><jats:italic>d<\/jats:italic><\/jats:sub> geometry is a minimum at both the HF and MP2 levels. This is not the case at definitive higher levels. The C<jats:sub>3<\/jats:sub>H<jats:sub>4<\/jats:sub><jats:sup>2+<\/jats:sup> structure with an apical H is another example of the failure of the calculations with the 6\u201031G**, 6\u2010311G**, and D95(<jats:italic>d<\/jats:italic>,<jats:italic>p<\/jats:italic>) basis sets. Even at MP2\/6\u201031G** and MP2\/ cc\u2010<jats:italic>p<\/jats:italic>VDZ levels, the <jats:italic>C<\/jats:italic><jats:sub>3<jats:italic>v<\/jats:italic><\/jats:sub> structure has no negative eigenvalues of the Hessian. Actually, this form is a second\u2010order saddle point as shown by the MP2\/6\u201031G** calculation with the optimized exponent. The <jats:italic>D<\/jats:italic><jats:sub>4<jats:italic>h<\/jats:italic><\/jats:sub> methane dication structure is also an example of the misleading performance of the 6\u201031G** basis set. In all these cases, energy\u2010optimized hydrogen <jats:italic>p<\/jats:italic> exponents give the correct results, i.e., those found with more extended treatments. Optimized values of the hydrogen polarization function exponents eliminate these defects in 6\u201031G** calculations. Species with higher coordinate hydrogens may also be calculated reliably by using more than one set of <jats:italic>p<\/jats:italic> functions on hydrogen [e.g., the 6\u201031G(<jats:italic>d<\/jats:italic>,2<jats:italic>p<\/jats:italic>) basis set]. Not all cases are critical. A survey of examples, also including some boron compounds, provides calibration. \u00a9 1993 John Wiley &amp; Sons, Inc.<\/jats:p>","DOI":"10.1002\/jcc.540140305","type":"journal-article","created":{"date-parts":[[2005,1,2]],"date-time":"2005-01-02T00:38:59Z","timestamp":1104626339000},"page":"285-294","source":"Crossref","is-referenced-by-count":17,"title":["Is tetrahedral H<sub>4<\/sub><sup>2+<\/sup> a minimum? 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