On Emerging Fields of Quantum Chemistry at Finite Temperature

Abstract

In this article, we present an emerging field of quantum chemistry at finite temperature. We discuss its recent developments on both theoretical and experimental fronts.We describe and analyze several experimental investigations related to the temperature effects on the structure, electronic spectra,or bond rupture forces for molecules. This includes the study of the temperature impact on the pathway shifts for the protein unfolding by atomic force microscopy, the temperature dependence of the absorption spectra of electrons in solvents, and temperature influence over the intermolecular forces measured by the AFM. On the theoretical side, we review a recent advancement made by the author in the coming fields of quantum chemistry at finite temperature. Starting from Bloch equation, we have derived the sets of hierarchy equations for the reduced density operators in both canonical and grand canonical ensembles. They provide a law according to which the reduced density operators vary in temperature for the identical and interacting many-body particles. By taking the independent particle approximation, we have solved the equation in the case of a grand canonical ensemble, and obtained an eigenequation for the molecular orbitals at finite temperature. The explicit expression for the temperature-dependent Fock operator is also given. They will form a foundation for the study of the molecular electronic structures and their interplay with the finite temperature. Furthermore, we clarify the physics concerning the temperature effect on the electronic structure or processes of molecules which is crucial for both theoretical understanding and computational study.Finally,we summarize our discussion and point out the theoretical and computational issues for the future explorations in the fields of quantum chemistry at finite temperature.