Static field-gradient polarizabilities of small atoms and molecules in finite temperature

Abstract

In this work, we propose new field-free estimators for static field-gradient polarizabilities in finite temperature PIMC simulation. Namely, dipole--quadrupole polarizability $A$, dipole--dipole--quadrupole polarizability $B$ and quadrupole--quadrupole polarizability $C$ are computed for several up to two-electron systems: H, H${}^{-}$, He, Li${}^{+}$, Be${}^{2+}$, Ps${}_2$, PsH, H${}_2^{+}$, H${}_2$, H${}_3^{+}$ and HeH${}^{+}$. We provide complementary data for ground state electronic properties within the adiabatic approximation, and demonstrate good agreement with available values in the literature. More importantly, we present fully non-adiabatic results from 50 K to 1600 K, which allow us to analyze and discuss strong thermal coupling and rovibrational effects in total field-gradient polarizabilities. These phenomena are most relevant but clearly overlooked, e.g., in the construction of modern polarizable force field models. However, our main purpose is demonstrating the accuracy and simplicity of our approach in a problem that is generally challenging.

arXiv comment6 pages, 2 figures, 2 supplementary pages

References in corpus (8)

• Accounting for electronic polarization in nonpolarizable force fields
• Theory and applications of atomic and ionic polarizabilities
• Accurate Born-Oppenheimer potential for HeH+
• High-precision nonadiabatic calculations of dynamic polarizabilities and hyperpolarizabilities for the lowlying vibrational-rotational states of hydrogen molecular ions
• Finite temperature quantum statistics of H${}_3^{+}$ molecular ion
• The H${}_2^{+}$ molecular ion: a solution
• The ground state of the ${\mathrm{H}}_3^{+}$ molecular ion: physics behind
• Hydrogen molecule ion: Path integral Monte Carlo approach

Cited by in corpus (2)

• Shell-confined atom and plasma: incidental degeneracy, metallic character and information entropy
• Path Integrals: From Quantum Mechanics to Photonics