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Full-Text Articles in Physical Sciences and Mathematics
Structure, Energetics, And Vibrational Spectrum Of H2o–Hcl, Z. Latajka, Steve Scheiner
Structure, Energetics, And Vibrational Spectrum Of H2o–Hcl, Z. Latajka, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
H2O–HCl is studied using a number of basis sets including 6‐31G∗∗ and variants which are augmented by a diffuse sp shell and a second set of d functions on O and Cl. Optimization of the geometry of the complex is carried out including explicitly electron correlation and counterpoise correction of the basis set superposition error (BSSE) at both the SCF and correlated levels. Correlation strengthens and shortens the H bond while BSSE correction leads to an opposite trend; these two effects are of different magnitude and hence cancel one another only partially. ΔH°(298 K) is …
Primary And Secondary Basis Set Superposition Error At The Scf And Mp2 Levels. H3n‐‐Li+ And H2o‐‐Li+, Z. Latajka, Steve Scheiner
Primary And Secondary Basis Set Superposition Error At The Scf And Mp2 Levels. H3n‐‐Li+ And H2o‐‐Li+, Z. Latajka, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The primary basis set superposition error (BSSE) results from the artificial lowering of the energy of each subunit of a pair by the presence of ‘‘ghost orbitals’’ of its partner. In addition, these ghost orbitals perturb the one‐electron properties of the molecule, causing a change in the interaction energy, an effect known as secondary BSSE which is not corrected by the counterpoise procedure. The primary and secondary BSSE are calculated for the interactions of NH3 and H2O with Li+, using a variety of different basis sets. It is found that the 2° BSSE can be …
Vibrational Frequencies And Intensities Of H-Bonded Systems. 1:1 And 1:2 Complexes Of Nh3 And Ph3 With Hfvibrational Frequencies And Intensities Of H‐Bonded Systems. 1:1 And 1:2 Complexes Of Nh3 And Ph3 With Hf, I. J. Kurnig, M. M. Szczesniak, Steve Scheiner
Vibrational Frequencies And Intensities Of H-Bonded Systems. 1:1 And 1:2 Complexes Of Nh3 And Ph3 With Hfvibrational Frequencies And Intensities Of H‐Bonded Systems. 1:1 And 1:2 Complexes Of Nh3 And Ph3 With Hf, I. J. Kurnig, M. M. Szczesniak, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
Frequencies and intensities are calculated by ab initio methods for all vibrational modes of the 1:1 H3X–HF and 1:2 H3X–HF–HF complexes (X=N,P). The HF stretching frequencies are subject to red shifts, roughly proportional to the strength of the H bond, and to manyfold increases in intensity. Although the intramolecular frequency shifts within the proton acceptors are relatively modest, the intensities of the NH3 stretches are magnified by several orders of magnitude as a result of H bonding (in contrast to PH3 which exhibits little sensitivity in this regard). …