Hydrogen molecule in a magnetic field: The lowest states of the Pi manifold and the global ground state of the parallel configuration

Abstract

The electronic structure of the hydrogen molecule in a magnetic field is investigated for parallel internuclear and magnetic field axes. The lowest states of the $Π$ manifold are studied for spin singlet and triplet$(M_s = -1) $ as well as gerade and ungerade parity for a broad range of field strengths $0 \leq B \leq 100 a.u.$ For both states with gerade parity we observe a monotonous decrease in the dissociation energy with increasing field strength up to $B = 0.1 a.u.$ and metastable states with respect to the dissociation into two H atoms occur for a certain range of field strengths. For both states with ungerade parity we observe a strong increase in the dissociation energy with increasing field strength above some critical field strength $B_c$. As a major result we determine the transition field strengths for the crossings among the lowest $^1Σ_g$, $^3Σ_u$ and $^3Π_u$ states. The global ground state for $B \lesssim 0.18 a.u.$ is the strongly bound $^1Σ_g$ state. The crossings of the $^1Σ_g$ with the $^3Σ_u$ and $^3Π_u$ state occur at $B \approx 0.18$ and $B \approx0.39 a.u.$, respectively. The transition between the $^3Σ_u$ and $^3Π_u$ state occurs at $B \approx 12.3 a.u.$ Therefore, the global ground state of the hydrogen molecule for the parallel configuration is the unbound $^3Σ_u$ state for $0.18 \lesssim B \lesssim 12.3 a.u.$ The ground state for $B \gtrsim 12.3 a.u.$ is the strongly bound $^3Π_u$ state. This result is of great relevance to the chemistry in the atmospheres of magnetic white dwarfs and neutron stars.