TY - JOUR

T1 - Classical Nuclear Motion

T2 - Comparison to Approaches with Quantum Mechanical Nuclear Motion

AU - Frank, Irmgard

N1 - Funding Information: Part of the calculations were performed on the local cluster of the Leibniz University of Hannover at the Leibniz University IT Services (LUIS).

PY - 2022/12/29

Y1 - 2022/12/29

N2 - Ab initio molecular dynamics combines a classical description of nuclear motion with a density-functional description of the electronic cloud. This approach nicely describes chemical reactions. A possible conclusion is that a quantum mechanical description of nuclear motion is not needed. Using Occam’s razor, this means that, being the simpler approach, classical nuclear motion is preferable. In this paper, it is claimed that nuclear motion is classical, and this hypothesis will be tested in comparison to methods with quantum mechanical nuclear motion. In particular, we apply ab initio molecular dynamics to two photoreactions involving hydrogen. Hydrogen, as the lightest element, is often assumed to show quantum mechanical tunneling. We will see that the classical picture is fully sufficient. The quantum mechanical view leads to phenomena that are difficult to understand, such as the entanglement of nuclear motion. In contrast, it is easy to understand the simple classical picture which assumes that nuclear motion is steady and uniform unless a force is acting. Of course, such a hypothesis must be verified for many systems and phenomena, and this paper is one more step in this direction.

AB - Ab initio molecular dynamics combines a classical description of nuclear motion with a density-functional description of the electronic cloud. This approach nicely describes chemical reactions. A possible conclusion is that a quantum mechanical description of nuclear motion is not needed. Using Occam’s razor, this means that, being the simpler approach, classical nuclear motion is preferable. In this paper, it is claimed that nuclear motion is classical, and this hypothesis will be tested in comparison to methods with quantum mechanical nuclear motion. In particular, we apply ab initio molecular dynamics to two photoreactions involving hydrogen. Hydrogen, as the lightest element, is often assumed to show quantum mechanical tunneling. We will see that the classical picture is fully sufficient. The quantum mechanical view leads to phenomena that are difficult to understand, such as the entanglement of nuclear motion. In contrast, it is easy to understand the simple classical picture which assumes that nuclear motion is steady and uniform unless a force is acting. Of course, such a hypothesis must be verified for many systems and phenomena, and this paper is one more step in this direction.

KW - Car–Parrinello molecular dynamics

KW - chemical reactions

KW - classical nuclear motion

KW - photoreactions

UR - http://www.scopus.com/inward/record.url?scp=85172764177&partnerID=8YFLogxK

U2 - 10.3390/hydrogen4010002

DO - 10.3390/hydrogen4010002

M3 - Article

VL - 4

SP - 11

EP - 21

JO - Hydrogen

JF - Hydrogen

SN - 2673-4141

IS - 1

ER -