Equilibrium Chemistry in $${\text {BCl}}_3$$ BCl 3 – $${\text {H}}_2$$ H 2

Electronic Free Energy Surface of the Nitrogen Dimer Using First-Principles Finite Temperature Electronic Structure Methods

“…The Helmholtz free energy is an important thermodynamic quantity that can be used to describe chemical processes. A part of this is the electronic free energy and consideration of this quantity is important in solid state materials, − spin-crossover systems, and in some cases, other molecular behavior. − In the case of solids it is well-known that the electronic free energy alone can be a significant contribution in the accurate description for the material. − On the other hand, the importance of electronic temperature in molecules has been demonstrated for specific situations such as spin-crossovers and at high temperatures. ,,, However, there is a need for more work to be done to fully understand the scope of how and when electronic temperature matters in molecules . One way to explore the scope is through ab initio electronic structure calculations.…”