A path integral molecular dynamics study on the NH4+ rotation in NH4+MIDLINE HORIZONTAL ELLIPSISXH2 (X = Be or Mg) dihydrogen bond systems

The nuclear quantum effects (NQEs) in dihydrogen bond (DHB) complexes, i.e., NH4+MIDLINE HORIZONTAL ELLIPSISBeH2 and NH4+MIDLINE HORIZONTAL ELLIPSISMgH2, have been investigated using multicomponent quantum mechanics (MC_QM) calculations and path integral molecular dynamics (PIMD) simulation. The MC_QM method considers the NQEs, whereas PIMD considers both the NQEs and the thermal effects. The linear C-3v structure is maintained in the optimized structures obtained by the static MP2 and MC_MP2 calculations, whereas the average structures obtained by the PIMD simulation are nonlinear. The strong DHB interaction in NH4+MIDLINE HORIZONTAL ELLIPSISMgH2 suppresses the fluctuation in the H delta+NMg and H delta-MgN angles, and hence, the NH4+ rotation did not occur in the simulation of NH4+MIDLINE HORIZONTAL ELLIPSISMgH2. The analysis of the radius of gyration revealed that the nuclear quantum fluctuation in the perpendicular direction is suppressed by the formation of the DHB complex, whereas that in the parallel direction is slightly enhanced in both the H delta+ and H delta- nuclei.

Automated summary

This study investigates the nuclear quantum effects (NQEs) and thermal effects in dihydrogen bond (DHB) complexes through calculations and simulations. It is found that the formation of DHB complexes suppresses quantum fluctuations in the perpendicular direction, but slightly enhances it in the parallel direction.