Testing the limitations of harmonic approximation in the determination of Raman intensities

Abstract

T2 Polarizability components (α ⊥ and α ∥ ) and invariants (ᾱ and γ) of HF calculated with CCSD(T) methodology and aug-cc-pwCVQZ AO basis. All values are in atomic units. . . . . . . . . . . . . . . . . . . T3 Polarizability components (α ⊥ and α ∥ ) and invariants (ᾱ and γ) of HF calculated with with CCSD(T) methodology and aug-cc-pwCVQZ AO basis, along with one 5p4d3f bond-function basis. All values are in atomic units. For more details on the exponents of the bond-functions and their location, refer to the Sec.

Ab Initio Vibro-Polaritonic Spectra in Strongly Coupled Cavity-Molecule Systems

“…Moreover, the | a c | 2 values of LP and UP are, besides the overall anharmonic shift, in very good agreement between the harmonic approximation and the full anharmonic treatment. Overall, we can conclude that for the coupling strengths studied, the semiclassical harmonic approximation qualitatively reproduces the features of the vibro-polaritonic IR spectra well, even for a highly anharmonic molecule such as HF, except for the well-known general limitation of the harmonic approximation. , …”

“…Overall, we can conclude that for the coupling strengths studied, the semiclassical harmonic approximation qualitatively reproduces the features of the vibro-polaritonic IR spectra well, even for a highly anharmonic molecule such as HF, except for the well-known general limitation of the harmonic approximation. 54 , 55 …”