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Full-Text Articles in Physical Sciences and Mathematics
Theoretical Vibrational Study Of Fx...Nh3 (X=H, D, Li) Complexes, Y. Bouteiller, Z. Latajka, H. Ratajczak, Steve Scheiner
Theoretical Vibrational Study Of Fx...Nh3 (X=H, D, Li) Complexes, Y. Bouteiller, Z. Latajka, H. Ratajczak, Steve Scheiner
Steve Scheiner
This paper presents the first ab initio attempt to construct the stretching fundamentals νFX and νF...N (X=H, D, Li) in the FX...NH3 complexes taking into account the mechanical anharmonicity. A potential‐energy surface V(rFX,RF...N) grid was generated at the self‐consistent‐field and second‐order Møller–Plesset levels. The coefficients fitting the potential‐energy surface up to the fourth order have been used to compute the νFX and νF...N stretching modes. The vibrational problem is solved by means of a variational treatment which includes the effects of mechanical …
Vibrational Frequencies And Intensities Of H‐Bonded And Li‐Bonded Complexes. H3n⋅⋅Hcl And H3n⋅⋅Licl, M. M. Szczesniak, I. J. Kurnig, Steve Scheiner
Vibrational Frequencies And Intensities Of H‐Bonded And Li‐Bonded Complexes. H3n⋅⋅Hcl And H3n⋅⋅Licl, M. M. Szczesniak, I. J. Kurnig, Steve Scheiner
Steve Scheiner
The geometries, energetics, and vibrational spectra are calculated for the two complexes at the SCF and correlated MP2 levels using the 6‐31G∗∗ basis set, augmented by a second set of d functions on Cl. While correlation represents an important factor in the binding of H3 N⋅⋅HCl, it contributes little to the stronger Li bond. Unlike the HCl stretch νs which decreases substantially in frequency and is greatly intensified in H3 N⋅⋅HCl, the frequency of the LiCl stretch undergoes an increase and little change is noted in its intensity, conforming to prior spectral measurements. The intensities of the …
Vibrational 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 Hf, I. J. Kurnig, M. M. Szczesniak, Steve Scheiner
Steve Scheiner
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). …