Enhanced shadow tomography of molecular excited states via the enforcement of N -representability conditions by semidefinite programming
Irma Avdic, David A. Mazziotti · Physical Review A · 2024
Excited-state properties of highly correlated systems are key to understanding photosynthesis, luminescence, and the development of novel optical materials, but accurately capturing their interactions is computationally costly. We present an algorithm that combines classical shadow tomography with physical constraints on the two-electron reduced density matrix (2RDM) to treat excited states. The method reduces the number of measurements of the many-electron 2RDM on quantum computers by (i) approximating the quantum state through a random sampling technique called shadow tomography and (ii) ensuring that the 2RDM represents an $N$-electron system through imposing $N$-representability constraints by semidefinite programming. This generalizes recent work on the $N$-representability-enhanced shadow tomography of ground-state 2RDMs. We compute excited-state energies and 2RDMs of the ${\mathrm{H}}_{4}$ chain and analyze the critical points along the photoexcited reaction pathway from gauche-1,3-butadiene to bicyclobutane via a conical intersection. The results show that the generalized shadow tomography retains critical multireference correlation effects while significantly reducing the number of required measurements, offering a promising avenue for the efficient treatment of electronically excited states on quantum devices.