Higher-order diagrammatic vibrational coupled-cluster theory.

Diagrammatically size-consistent and basis-set-free vibrational coupled-cluster (XVCC) theory for both zero-point energies and transition frequencies of a molecule, the latter through the equation-of-motion (EOM) formalism, is defined for an nth-order Taylor-series potential energy surface (PES). Quantum-field-theoretical tools (the rules of normal-ordered second quantization and Feynman-Goldstone diagrams) for deriving their working equations are established. The equations of XVCC and EOM-XVCC including up to the mth-order excitation operators are derived and implemented with the aid of computer algebra in the range of 1 ≤ m ≤ 8. Algorithm optimizations known as strength reduction, intermediate reuse, and factorization are carried out before code generation, reducing the cost scaling of the mth-order XVCC and EOM-XVCC in an nth-order Taylor-series PES (m ≥ n) to the optimal value of O(N(m+⌊n/2⌋)), where N is the number of modes. The calculated zero-point energies and frequencies of fundamentals, overtones, and combinations as well as Fermi-resonant modes display rapid and nearly monotonic convergence with m towards the exact values for the PES. The theory with the same excitation rank as the truncation order of the Taylor-series PES (m = n) seems to strike the best cost-accuracy balance, achieving the accuracy of a few tenths of cm(-1) for transitions involving (m - 3) modes and of a few cm(-1) for those involving (m - 2) modes. The relationships between XVCC and the vibrational coupled-cluster theories of Prasad and coworkers and of Christiansen and coworkers as well as the size-extensive vibrational self-consistent-field and many-body perturbation theories are also elucidated.