Quantum tunneling splittings from path-integral molecular dynamics.
نویسندگان
چکیده
We illustrate how path-integral molecular dynamics can be used to calculate ground-state tunnelling splittings in molecules or clusters. The method obtains the splittings from ratios of density matrix elements between the degenerate wells connected by the tunnelling. We propose a simple thermodynamic integration scheme for evaluating these elements. Numerical tests on fully dimensional malonaldehyde yield tunnelling splittings in good overall agreement with the results of diffusion Monte Carlo calculations.
منابع مشابه
Spin Tunneling in Molecular Magnets
We study spin tunneling in magnetic molecules, with special reference to Fe8. The article aims to give a pedagogical discussion of what is meant by the tunneling of a spin, and how tunneling amplitudes or energy level splittings may be calculated using path integral and discrete phase integral methods. In the case of Fe8, an issue of great interest is the oscillatory tunnel splittings as a func...
متن کاملDriven quantum tunneling
A contemporary review on the behavior of driven tunneling in quantum systems is presented. Diverse phenomena, such as control of tunneling, higher harmonic generation, manipulation of the population dynamics and the interplay between the driven tunneling dynamics and dissipative effects are discussed. In the presence of strong driving fields or ultrafast processes, well-established approximatio...
متن کاملQuantum nature of the hydrogen bond
Hydrogen bonds are weak, generally intermolecular bonds, which hold much of soft matter together as well as the condensed phases of water, network liquids, and many ferroelectric crystals. The small mass of hydrogen means that they are inherently quantum mechanical in nature, and effects such as zero-point motion and tunneling must be considered, though all too often these effects are not consi...
متن کاملCorrection: "On-the-fly" coupled cluster path-integral molecular dynamics: impact of nuclear quantum effects on the protonated water dimer.
We present an accelerated ab initio path-integral molecular dynamics technique, where the interatomic forces are calculated "on-the-fly" by accurate coupled cluster electronic structure calculations. In this way not only dynamic electron correlation, but also the harmonic and anharmonic zero-point energy, as well as tunneling effects are explicitly taken into account. This method thus allows fo...
متن کاملCombined QM/MM and path integral simulations of kinetic isotope effects in the proton transfer reaction between nitroethane and acetate ion in water
An integrated Feynman path integral-free energy perturbation and umbrella sampling (PI-FEP/UM) method has been used to investigate the kinetic isotope effects (KIEs) in the proton transfer reaction between nitroethane and acetate ion in water. In the present study, both nuclear and electronic quantum effects are explicitly treated for the reacting system. The nuclear quantum effects are represe...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- The Journal of chemical physics
دوره 144 11 شماره
صفحات -
تاریخ انتشار 2016