Laboratorium fur Physikalische Chemie, ETH-Zürich, Switzerland.
J Chem Phys. 2010 Apr 21;132(15):154301. doi: 10.1063/1.3374426.
The transition wave numbers from selected rovibrational levels of the EF (1)Sigma(g) (+)(v=0) state to selected np Rydberg states of ortho- and para-D(2) located below the adiabatic ionization threshold have been measured at a precision better than 10(-3) cm(-1). Adding these wave numbers to the previously determined transition wave numbers from the X (1)Sigma(g) (+)(v=0, N=0,1) states to the EF (1)Sigma(g) (+)(v=0, N=0,1) states of D(2) and to the binding energies of the Rydberg states calculated by multichannel quantum defect theory, the ionization energies of ortho- and para-D(2) are determined to be 124 745.394 07(58) cm(-1) and 124 715.003 77(75) cm(-1), respectively. After re-evaluation of the dissociation energy of D(2) (+) and using the known ionization energy of D, the dissociation energy of D(2) is determined to be 36 748.362 86(68) cm(-1). This result is more precise than previous experimental results by more than one order of magnitude and is in excellent agreement with the most recent theoretical value 36 748.3633(9) cm(-1) [K. Piszczatowski, G. Łach, M. Przybytek et al., J. Chem. Theory Comput. 5, 3039 (2009)]. The ortho-para separation of D(2), i.e., the energy difference between the N=0 and N=1 rotational levels of the X (1)Sigma(g) (+)(v=0) ground state, has been determined to be 59.781 30(95) cm(-1).
已在优于 10^(-3) cm^(-1)的精度下测量了从 EF(1)Sigma(g)^+(v=0)态的选定振转能级到位于绝热电离阈值以下的 o-和 p-D(2)的选定 np 里德堡态的跃迁波数。将这些波数与之前从 X(1)Sigma(g)^+(v=0, N=0,1)态到 D(2)的 EF(1)Sigma(g)^+(v=0, N=0,1)态的跃迁波数以及多通道量子亏损理论计算的里德堡态的结合能相加,确定 o-和 p-D(2)的电离能分别为 124745.39407(58) cm^(-1)和 124715.00377(75) cm^(-1)。在重新评估 D(2)^+(+)的离解能并使用已知的 D 电离能后,确定 D(2)的离解能为 36748.36286(68) cm^(-1)。该结果比以前的实验结果精确一个数量级以上,与最近的理论值 36748.3633(9) cm^(-1)[K. Piszczatowski, G. Łach, M. Przybytek 等人,J. Chem. Theory Comput. 5, 3039 (2009)]非常吻合。D(2)的 o-para 分离,即 X(1)Sigma(g)^+(v=0)基态的 N=0 和 N=1 转动能级之间的能量差,确定为 59.78130(95) cm^(-1)。