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HP−4: the monoconjugate base from tetraphosphabicyclobutane. Evidence for an exo ground state conformation in the gas phase

✍ Scribed by Tracy P. Hamilton; Yaoming Xie; Henry F. Schaefer III


Publisher
Elsevier Science
Year
1993
Tongue
English
Weight
420 KB
Volume
208
Category
Article
ISSN
0009-2614

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✦ Synopsis


Ab initio theoretical studies reconsider recent experimental findings concerning the ground state conformation of the HP; anion. Basis sets as large as triple zeta plus double polarization plus f functions plus diffuse functions (TZZPf+diffuse) were used in connection with methods that explicitly include the effects of electron correlation. At the highest level of theory, the exo structure is predicted IO lie about two kcal/mol below the endo structure, in apparent disagreement with experiment. The Li*HPI system has also been examined to approximate more closely the system synthesized in the laboratory. The energetics are signit% cantly shifted by the appendage of the Li+ cation, and the agreement between theory and experiment deteriorates further.