Accurate harmonic vibrational frequencies for diatomic molecules via quantum computing

During the noisy intermediate-scale quantum (NISQ) era, quantum computational approaches refined to overcome the challenge of limited quantum resources are highly valuable. However, the accuracy of the molecular properties predicted by most of the quantum computations nowadays is still far off (not within chemical accuracy) compared to their corresponding experimental data. Here, we propose a promising qubit-efficient quantum computational approach to calculate the harmonic vibrational frequencies of a large set of neutral closed-shell diatomic molecules with results in great agreement with their experimental data. To this end, we construct the accurate Hamiltonian using molecular orbitals, derived from density functional theory to account for the electron correlation and expanded in the Daubechies wavelet basis set to allow an accurate representation in real space grid points, where an optimized compact active space is further selected so that only a reduced small number of qubits is sufficient to yield an accurate result. To justify the approach, we benchmark the performance of the Hamiltonians spanned by the selected molecular orbitals by first transforming the molecular Hamiltonians into qubit Hamiltonians and then using the exact diagonalization method to calculate the results, regarded as the best results achievable by quantum computation. Furthermore, we show that the variational quantum circuit with the chemistry-inspired UCCSD ansatz can achieve the same accuracy as the exact diagonalization method except for systems whose Mayer bond order indices are larger than 2. For those systems, we demonstrate that the heuristic hardware-efficient RealAmplitudes ansatz, even with a shorter circuit depth, can provide a significant improvement over the UCCSD ansatz, verifying that the harmonic vibrational frequencies could be calculated accurately by quantum computation in the NISQ era.
Comment: 17 pages, 5 figures plus 11-page supplemental material