Abstract
This chapter offers an introductory theoretical treatment of the vibration aspects of the hydrogen bond. A hydrogen bonded system is characterized by the interaction of intra- and intermolecular forces. As a result a proper description of the corresponding vibrations can only be obtained from a quantummechanical treatment. This is illustrated in a pictorial way for the case of the stretching vibrations in a linear A-H-B system. Such a system exhibits a double-well potential, which deviates considerably from the classical two-dimensional harmonic oscillator. Solutions of the wave equation for nuclear motion in this potential are discussed, with special attention to the splitting effect of the double well and the coupling of the vs and νσ vibrations.
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References
Janoschek R (1976) In: Schuster P, Zundel G, Sandorfy C (eds) The hydrogen bond Part I: Theory. North-Holland, Amsterdam, chap 3
The lower-diagonal element of the ℝ matrix in equation 10 is equal to the scalar product 〈Qσ|Qy〉. The inverse cosine of this term thus yields the desired angle.
Somorjai RL, Hornig DF (1962) J Chem Phys 36: 1980
Busch JH, de la Vega JR (1977) J Am Chem Soc 99: 2397
Flanigan MC, de la Vega JR (1974) J Chem Phys 61: 1882
Manning MF (1935) J Chem Phys 3: 136
The outer sech2 well is also known as the Pöschl-Teller hole; see Poschl G, Teller E (1933) Z Phys 83: 143
Herzberg G (1945) Molecular Spectra and Molecular Structure II Infrared and Raman Spectra of Polyatomic Molecules. Van Nostrand, Princeton NJ, p 222
Swalen JD, Ibers JA (1962) J Chem Phys 36: 1914
Papousek D, Stone JMR, Spirko V (1973) J Mol Spectrosc 48: 17
Notice that the symmetric level |0 + 〉 is always at lower energy than the antisymmetric |0– 〉 level. This is because the latter level has a nodal point in the origin, which keeps the function away from the saddle region. As a result it hits the outer walls at higher energies.
The experimental observation of this tunneling splitting constituted an important test for the validity of the wave-mechanical treatment
Ginn SGW, Wood JL (1967) J Chem Phys 46: 2735
Romanowski H, Sobczyk L (1977) Chem Phys 19: 361
Sandorfy C (1984) Top Curr Chem 120: 41
Brickmann J (1976) In: Schuster P, Zundel G, Sandorfy C (eds) The hydrogen bond Part I: Theory. North-Holland, Amsterdam, chap 4
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© 1991 Springer-Verlag Berlin, Heidelberg
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Ceulemans, A. (1991). Vibration Aspects of the Hydrogen Bond. In: Huyskens, P.L., Luck, W.A.P., Zeegers-Huyskens, T. (eds) Intermolecular Forces. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-76260-4_5
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DOI: https://doi.org/10.1007/978-3-642-76260-4_5
Publisher Name: Springer, Berlin, Heidelberg
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