Determination of fundamental properties of nitrogen from first principles. III. Temperature and frequency dependence of the molecular polarizability and magnetic susceptibility

This work is the third part of the series of papers that focus on the theoretical determination of the properties of nitrogen that are relevant in metrology. Here, we present first-principles calculations of the temperature and frequency dependence of the molecular polarizability and magnetic susceptibility of the nitrogen molecule (N2). The purely electronic contributions to the static polarizability, Cauchy coefficients (up to sixth order), and isotropic magnetic susceptibility are computed over a range of internuclear distances using a robust composite scheme combining several electronic structure methods. The temperature dependence, evaluated from 50 to 2000 K, is determined using two independent methods: rovibrational averaging and path integral Monte Carlo. The polarizabilities obtained from theory agree with the recent high-precision thermometry measurements, wherever the latter are available, but are significantly less accurate. However, the main usefulness of the theoretical data revolves around combining it with the available experimental results to generate semi-empirical estimates of various quantities that have never been measured thus far. As an example, we determine highly accurate semi-empirical estimates of the static polarizability at key reference temperatures, α0(T) = 11.735 962 a.u. at T = 303 K and α0(T) = 11.735 585 a.u. at T = 273.16 K. Furthermore, we report theoretical values for the magnetic susceptibility, highlighting the importance of the paramagnetic contribution, and address a significant discrepancy with the experimental data for this quantity.