10.10 Anharmonic Vibrational Frequencies

10.10.2 Vibrational Perturbation Theory

(May 16, 2021)

Vibrational perturbation theory has been historically popular for calculating molecular spectroscopy. Nevertheless, it is notorious for the inability of dealing with resonance cases. In addition, the non-standard formulas for various symmetries of molecules forces the users to modify inputs on a case-by-case basis, 35 Allen W. D. et al.
Chem. Phys.
(1990), 145, pp. 427.
Link
, 205 Clabo D. A. et al.
Chem. Phys.
(1988), 123, pp. 187.
Link
which narrows the accessibility of this method. VPT applies perturbation treatments on the same Hamiltonian as in Eq. (4.1), but divides it into an unperturbed part, U^,

U^=im(-122qi2+ωi22qi2) (10.44)

and a perturbed part, V^:

V^=16ijk=1mηijkqiqjqk+124ijkl=1mηijklqiqjqkql (10.45)

One can then apply second-order perturbation theory to get the ith excited state energy:

E(i)=U^(i)+Ψ(i)|V^|Ψ(i)+ji|Ψ(i)|V^|Ψ(j)|2U^(i)-U^(j) (10.46)

The denominator in Eq. (10.46) can be zero either because of symmetry or accidental degeneracy. Various solutions, which depend on the type of degeneracy that occurs, have been developed which ignore the zero-denominator elements from the Hamiltonian. 797 Nielsen H. H.
Rev. Mod. Phys.
(1951), 23, pp. 90.
Link
, 35 Allen W. D. et al.
Chem. Phys.
(1990), 145, pp. 427.
Link
, 205 Clabo D. A. et al.
Chem. Phys.
(1988), 123, pp. 187.
Link
An alternative solution has been proposed by Barone, 62 Barone V.
J. Chem. Phys.
(2005), 122, pp. 014108.
Link
which can be applied to all molecules by changing the masses of one or more nuclei in degenerate cases. The disadvantage of this method is that it will break the degeneracy which results in fundamental frequencies no longer retaining their correct symmetry. He proposed

EiVPT2=jωj(nj+1/2)+ijxij(ni+1/2)(nj+1/2) (10.47)

where, if rotational coupling is ignored, the anharmonic constants xij are given by

xij=14ωiωj(ηiijj-kmηiikηjjkωk2+km2(ωi2+ωj2-ωk2)ηijk2[(ωi+ωj)2-ωk2][(ωi-ωj)2-ωk2]) (10.48)