Université Paris-Est, Laboratoire Modélisation et Simulation Multi-Echelle (MSME), UMR 8208 CNRS, 5 bd Descartes, 77454 Marne la Vallée, France.
J Chem Phys. 2017 Sep 21;147(11):114111. doi: 10.1063/1.4998467.
Theoretical spectroscopic parameters are derived for all isotopologues of HCO and HOC involving H, D, O, O, O, C, and C 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, ν, ν, and ν 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(CH) = 1.091 98 Å and r(CO) = 1.105 62 Å, and for the equilibrium structure of HOC, r(HO) = 0.990 48 Å and r(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 is within 3 MHz, for the quartic centrifugal distortion constants D within 1 kHz, and for the effective ℓ-doubling constants q 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.
通过两步程序，为所有涉及 H、D、O、O、O、C 和 C 的 HCO 和 HOC 同位素异构体推导了理论光谱参数。首先进行全维振转计算，以获得两种宇称中 J = 0-15 的数值精确振转能量。通过将计算出的振转能量拟合到适当的光谱哈密顿量，确定振动基态 ν、ν、和 ν 的有效光谱常数。结合我们的振动-旋转修正以及可用的实验基态旋转常数，我们还推导出 HCO 的平衡结构的新估计值，r(CH) = 1.091 98 Å 和 r(CO) = 1.105 62 Å，以及 HOC 的平衡结构的新估计值，r(HO) = 0.990 48 Å 和 r(CO) = 1.154 47 Å。关于光谱参数，我们的估计与 HCO 和 HOC 的同位素变体的可用实验结果非常吻合：旋转常数 B 的吻合度在 3 MHz 以内，四次离心畸变常数 D 的吻合度在 1 kHz 以内，有效 ℓ-双重常数 q 的吻合度在 2 MHz 以内。因此，我们预计我们的结果可以为尚未通过实验得知的 HCO 和 HOC 的稀有同位素异构体的预期观测提供有用的帮助。
