On the Physical Consistency of an Open Quantum Region with a Classical Reservoir in Molecular Simulation

The possibility of treating a molecular liquid in an open region at ab initio electronic resolution embedded in a classical reservoir of energy and particles, is investigated. Because of its challenging properties and its relevance in many field of current research, the system chosen as prototype of molecular liquid is water at room conditions. A numerical protocol based on the mathematical model of open particle system is applied and the results are compared with results of a full ab initio simulation of reference. The key conclusion is that one can claim the existence of a mandatory minimal size of the quantum region in which structural and electronic properties reproduce those of reference and, at the same time, the exchange of molecules with the environment takes place as expected. This work provides a proof of concept about the possibility to systematically define a physically well founded open quantum system embedded in a classical environment. In turn, the proof of concept is a key information for the design of numerically efficient algorithms for ab initio molecular dynamics simulations of open systems. In this work, the possibility of treating liquid water in an open region at ab initio electronic resolution embedded in a classical reservoir of energy and particles is studied. The results specify a (mandatory) minimal size of the open quantum region that is able to reproduce the structural and electronic properties of the reference calculated at full ab initio level. image