Statistical errors in reduced density matrices sampled from quantum circuit simulation and the impact on multireference perturbation theory.

In this work, we present a detailed analysis of statistical errors in reduced density matrices (RDMs) of active space wavefunctions sampled from quantum circuit simulation and the impact on results obtained by the multireference theories. From the sampling experiments, it is shown that the errors in sampled RDMs have a larger value for higher-order RDMs, and that the errors in sampled RDMs for excited states are larger than those for the ground state. We analytically derive the expected value of the sum of squared errors between the true distribution and sample distribution of weights of the electron configurations based on a multinomial distribution model, with which we present an assessment of the dependency of RDM errors on the number of shots for the observation ( N shot ) and on the character of the target electronic state. With the benchmark calculations of short polyenes, C 4 H 6 and C 6 H 8 , we report the statistical errors in CASCI and complete active space second-order perturbation theory (CASPT2) energies obtained with the sampled 1,2-RDMs and 1,2,3,4-RDMs, respectively. It was found that the standard deviation (SD) of the sampled CASCI energies is proportional to as predicted. It was also found that the dependence of the SD of the second-order correction energies are somewhat different but the errors in the reference CASCI energies are dominant as compared with the corrections and the SD of the resulting CASPT2 energies are proportional to . This suggests that the required N shot for 3,4-RDMs used only in the second-order perturbative corrections is smaller than that for 1,2-RDM used to calculate the reference CASCI energies. It was also suggested from the analysis of the errors in the sampled energies that the required N shot for 3-RDM, which is used to calculate the perturbative correction energies, can be smaller than that for 2-RDM to calculate the CASCI energies. In fact, it was shown that the potential energy curve along the isomerization reaction of the {[Cu(NH 3 ) 3 ] 2 O 2 } 2+ complex as an archetype of metalloenzyme, in which static and dynamical electron correlations are both important, can be reasonably reproduced with N shot = 10 6 for 1,2-RDMs but N shot = 10 5 for 3-RDM by the sampling simulation.