TY - JOUR
T1 - The effect of resonance on the force constants and lengths of chemical bonds
AU - Warhurst, E
PY - 1944
Y1 - 1944
N2 - The solution of the secular equation, which gives the energy of the actual state of a molecule in terms of the energies of the resonance states and a resonance integral, has been differentiated with respect to the internuclear separation for one of the bonds in the molecule. From the first differentiation, an equation has been derived which illustrates the effect of resonance on the bond length. This has been applied to two types of resonance, viz. between covalent single and double bonds, and to ionic-covalent resonance. The second differentiation gives an equation which shows the effect of resonance on the bond force constant. Using this equation, an explanation for the decrease in vibration frequency, which occurs when certain gases are liquefied or dissolved in non-ionising solvents, has been put forward. Calculations of the magnitude of this effect for the diatomic molecules HCl, HBr, HI, and H2 are in good agreement with the experimental facts.
AB - The solution of the secular equation, which gives the energy of the actual state of a molecule in terms of the energies of the resonance states and a resonance integral, has been differentiated with respect to the internuclear separation for one of the bonds in the molecule. From the first differentiation, an equation has been derived which illustrates the effect of resonance on the bond length. This has been applied to two types of resonance, viz. between covalent single and double bonds, and to ionic-covalent resonance. The second differentiation gives an equation which shows the effect of resonance on the bond force constant. Using this equation, an explanation for the decrease in vibration frequency, which occurs when certain gases are liquefied or dissolved in non-ionising solvents, has been put forward. Calculations of the magnitude of this effect for the diatomic molecules HCl, HBr, HI, and H2 are in good agreement with the experimental facts.
UR - http://www.scopus.com/inward/record.url?scp=37049172173&partnerID=8YFLogxK
M3 - Article
SN - 0014-7672
VL - 40
SP - 26
EP - 39
JO - Transactions of the Faraday Society
JF - Transactions of the Faraday Society
ER -