Abstract
The electronic and rovibrational structure of (1A1) NaH2 + has been investigated using a relativistically-corrected, all-electron coupled-cluster with singles, doubles and perturbative triples (CCSD(T)) ansatz. For the electronic ground state this ansatz yielded equilibrium Na–H bond lengths (R e ) of 2.4208 Å and an equilibrium H–Na–H bond angle (θe) of 17.8°. An analytical potential energy surface (PES) was embedded in the rovibrational Hamiltonian. The PES was constructed using 118 CCSD(T) points and exhibited a residual error of 1.2 cm−1. The rovibrational Hamiltonian was diagonalised using variational techniques. The vibrational and rovibrational eigenvectors were assigned using a configuration weight scheme in terms of normal modes and the Mulliken assignment scheme, respectively. For the ground vibrational state of (1A1) NaH2 +, the vibration-averaged bond lengths 〈R〉 and angle 〈θ〉 were 2.4995 Å and 17.1°, respectively. The ab initio (1A1) NaH2 + PES yielded a dissociation energy (D 0) value of 10.3 kJ mol−1, which is in excellent agreement with the experimental value of 10.3 ± 0.8 kJ mol−1 (Bushnell et al. in J Phys Chem 98:2044, 1994). An analytical dipole moment surface was constructed using 90 CCSD(T) points. Rovibrational spectra of (1A1) NaH2 +, (1A′) NaHD+ and (1A1) NaD2 + for v ≤ 10, J ≤ 5 were constructed using rovibrational transition moment matrix elements calculated in a novel manner that employs the analytical dipole moment surface (DMS). The rovibrational structure of the Na+–H2 v HH = 1 ← v HH = 0 band was calculated and compared to that of Li+–H2.
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Acknowledgments
The authors wish to acknowledge support from the Australian Partnership for Advanced Computing (APAC), the Australian Centre for Advanced Computing and Communications (AC3) and the high-performance computing facility of The University of Newcastle, Australia. A.J.P. wishes to acknowledge support from the Australian postgraduate award scheme.
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Page, A.J., von Nagy-Felsobuki, E.I. Ab Initio rovibrational spectrum of the NaH2 + ion–quadrupole complex. Theor Chem Account 122, 87–100 (2009). https://doi.org/10.1007/s00214-008-0487-7
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DOI: https://doi.org/10.1007/s00214-008-0487-7