Nuclear quantum and H/D isotope effects on three-centered bonding diborane: Path integral molecular dynamics simulations

Abstract

© 2020 Wiley Periodicals, Inc. Nuclear quantum and H/D isotope effects of bridging and terminal hydrogen atoms of diborane (B2H6) molecules were systematically studied by classical ab initio molecular dynamics (CLMD) and ab initio path integral molecular dynamics (PIMD) simulations with BHandHLYP/6-31++G** level of theory at room temperature (298.15 K). Calculated results clearly show that H/D isotope effect appears in the distribution of hydrogen (deuterium) of B2H6 (B2D6). Geometry of B2H6 also plays a significant role in the nuclear quantum effect proved by PIMD simulations, but slightly deviated from its equilibrium structure when simulated via CLMD simulation. The bond lengths between boron atoms R (B1 … B2) and the bridging hydrogen atoms RHH (HB1 … HB2) of the B2H6 molecule obtained from PIMD simulations are slightly longer than those of the deuterated form of the diborane (B2D6) molecule. The principal component analysis (PCA) was also employed to distinguish the important modes of bridging hydrogen as related to the nuclear quantum and H/D isotope effects. The highest level of contribution obtained from PCA of PIMD simulations is bending, while various mixed vibrations with less contribution were also found. Therefore, the nuclear quantum and H/D isotope effects need to be taken into account for a better understanding of diborane geometry.