Résumé
Quantum computing has recently been emerging in theoretical chemistry as a realistic avenue meant to offer computational speedup to challenging eigenproblems in the context of strongly correlated molecular systems or extended materials. Most studies so far have been devoted to the quantum treatment of electronic structure, for which the transformation of fermionic operators into the qubit space is quite transparent. In contrast, only a few were directed to the quantum treatment of vibrational structure, and some specific issues remain to be underscored. When simulating an anharmonic vibrational mode under bosonic second quantization, the biggest problem, which we analyze in detail in the present work, is the nonfulfillment of the closure relation, i.e., the incomplete resolution of the identity, when truncating the infinite harmonic-oscillator basis set of primitive modals and how this alters the canonical commutation relation. This may lead to serious incorrectness in the evaluation of the Hamiltonian matrix elements when assembling them from finite matrix products, which eventually entail a nonvariational behavior with respect to the finite size of the computational basis. As we show here, a simple cure is found upon using Wick’s normal order, for reasons that are not its standard incentive. We also provide a detailed comparison between the boson-to-qubit unary and binary mappings under two different representations: one for the bosonic ladder operators within the harmonic-oscillator primitive basis and one for the so-called
n
-mode representation within any type of computational basis. In addition, we discuss the impact of choosing an adequate primitive basis set in terms of quantum computing with respect to its variational convergence efficiency (number of basis functions, hence of qubits) and as regards the magnitude of the 1-norm of the encoded Hamiltonian (a measure of the computational complexity of the quantum algorithm). Such fundamental aspects are illustrated numerically on a one-dimensional anharmonic Hamiltonian model corresponding to a symmetric double-well potential, of interest both for vibrational spectroscopy and chemical reactivity, and which is a challenging situation for numerical convergence due to fine tunneling splitting.