Theoretical spectroscopic parameters for isotopic variants of HCO⁺ and HOC

Theoretical spectroscopic parameters are derived for all isotopologues of HCO⁺ and HOC⁺ involving H, D, ¹⁶O, ¹⁷O, ¹⁸O, ¹²C, and ¹³C by means of a two-step procedure. Full-dimensional rovibrational calculations are first carried out to obtain numerically exact rovibrational energies for J = 0-15 in both parities. Effective spectroscopic constants for the vibrational ground state, ν₁, ν₂, and ν₃ are determined by fitting the calculated rovibrational energies to appropriate spectroscopic Hamiltonians. Combining our vibration-rotation corrections with the available experimental ground-state rotational constants, we also derive the new estimate for the equilibrium structure of HCO⁺, r_e(CH) = 1.091 98 Å and r_e(CO) = 1.105 62 Å, and for the equilibrium structure of HOC⁺, r_e(HO) = 0.990 48 Å and r_e(CO) = 1.154 47 Å. Regarding the spectroscopic parameters, our estimates are in excellent agreement with available experimental results for the isotopic variants of both HCO⁺ and HOC⁺: the agreement for the rotational constants B_v is within 3 MHz, for the quartic centrifugal distortion constants D_v within 1 kHz, and for the effective ℓ-doubling constants q_v within 2 MHz. We thus expect that our results can provide useful assistance in analyzing expected observations of the rare isotopologues of HCO⁺ and HOC⁺ that are not yet experimentally known.