All molecules are entangled in the number of electrons following a general physical principle

Abstract

A physically motivated equation that determines the number of electrons of a molecule is proposed based on some generally accepted basic chemical knowledge. It permits a complete local definition of molecules and shows that all molecules are entangled in the number of electrons. It also results in the extensivity and convexity of molecular energy, which underpin molecular quantum mechanics. The proposed physical principle includes the molecular size consistency principle as a special case and reveals an intrinsic relationship between molecular locality, size consistency, and energy convexity. Application of wavefunction theory to the new principle shows that an individual molecule with a noninteger number of electrons is locally physical. The energy of a molecule is piecewise linear with respect to its number of electrons. The realness of the number of electrons allows the definition of the electronic chemical potential of a single molecule. A state function equivalent to the energy of a molecule can be defined using the chemical potential as a variable and used to express the physical principle as a simple additivity. The latter also shows that the quantum entanglement in the number of electrons can be viewed as all molecules sharing one chemical potential. When the energy of a molecule with a definite number of electrons is not convex with respect to the number of electrons, the state of the molecule is not always locally determinable even with a known number of electrons.