Canonical quantum observables for molecular systems approximated by ab initio molecular dynamics (Q1783928)

The authors address the important question: How to modify the canonical ab initio molecular dynamics in order to accurately approximate quantum observables based on matrix-valued potentials and all temperatures. Molecular dynamics methods are derived to approximate a quantum observable in the case where the temperature can be large compared to the first spectral gap. The approximation consists of weighted sum of molecular dynamics observables for the scalar Hamiltonians which are the eigenvalues of the original matrix-valued Hamiltonian symbol. Furthermore, the weights, which are the probabilities to be in the corresponding electron states are determined precisely as molecular dynamics observables. The main result is that weighted sums of molecular dynamics observables approximate canonical quantum observables, based on Schrödinger Hamiltonians with matrix-valued potentials for any positive temperature.