David Bishop's approach to vibrational dynamic contributions to molecular properties: Application to Jones and magnetoelectric birefringences in diatomic molecules

Abstract

ABSTRACT:The expressions derived by D. M. Bishop for the pure vibrational contributions to the dynamic electric dipole polarizabilities and hyperpolarizabilities of polyatomic molecules (see Bishop, D. M. Rev Mod Phys, 1990, 62, 343) are generalized to arbitrary linear, quadratic and cubic response functions, and then applied to determine the effect of nuclear motion on two diatomic molecules (N 2 and CO) on Jones (and Magnetoelectric) linear birefringences. The influence of nuclear motion on the anisotropy of the refractive index appears to be quite contained: the observable differs from the equilibrium electronic estimate by ≈4% for N 2 , and by ≈8-9% in CO. As a case study, also the effect of vibrations on the temperature independent contribution to Buckingham birefringence of H 2 and D 2 is analyzed and discussed.

Recent Advances in Wave Function-Based Methods of Molecular-Property Calculations

“…Indeed, only properties with a quadratic dependence on the magnetic field exhibit pure vibrational corrections, such as the hypermagnetizability that determines the Cotton–Mouton effect. , Correlated calculations of pure vibrational contributions to hypermagnetizabilities have been presented . Rizzo and Cappelli also recently presented CCSD investigations of the pure vibrational contributions to EFGB and Jones birefringence …”

A density functional theory study of magneto-electric Jones birefringence of noble gases, furan homologues, and mono-substituted benzenes

“…2. In the meantime, aspects as the dependence on the accurate (beyond CC singles and doubles, CCSD 59 ) treatment of electron correlation, 60 the effect of molecular vibrations (in diatomics), 61 that of the environment, 62 or the dependence of the results of calculations performed in finite one-electron basis sets on the choice of the magnetic gauge origin 63 have been also studied. The theory of magnetoelectric Jones birefringence and dichroism was redrafted by Mironova and coworkers 64 a few years ago.…”