Transition metal tetrahalides are a class of highly symmetric molecules for which very few spectroscopic data exist. Exploratory ab initio calculations of electronic potential energy functions indicate that the equilibrium molecular geometries of the vanadium, niobium, and tantalum tetrafluorides (i.e., VF4, NbF4, and TaF4) exhibit strong distortions from the tetrahedral configuration in their electronic ground state (2E) and first excited state (2T2) along the nuclear displacement coordinates of e symmetry. The distortions result from the E × e and T2 × e Jahn–Teller (JT) effects, respectively. In addition, there are weaker distortions in the 2T2 state along the coordinates of t2 symmetry due to the T2 × t2 JT effect. The description of the large-amplitude dynamics induced by these JT effects requires the construction of JT Hamiltonians beyond the standard model of JT theory, which is based on Taylor expansions up to second order in normal-mode displacements. These higher-order JT Hamiltonians were constructed in this work by expansions of the electronic potentials of the title molecule in terms of symmetry invariant polynomials in symmetry-adapted nuclear displacement coordinates for the bending modes of VF4. A multi-configuration electronic structure method was employed to determine the coefficients of these high-order polynomial expansions from first principles. Using these large-amplitude Jahn–Teller Hamiltonians, the vibronic spectra of VF4 were computed. The spectra illustrate the effects of large-amplitude fluxional nonadiabatic dynamics due to exceptionally strong E × e and T2 × e JT couplings. In addition, the vibronic spectrum of the T2 × (e + t2) JT effect, including the bending mode of t2 symmetry, was computed. The spectrum displays strong inter-mode coupling effects exhibiting a vibronic structure, which is substantially different from that predicted by independent-mode approximation. These results represent the first ab initio study of dynamical Jahn–Teller effects in VF4.

The vibrational spectra of group 12 difluorides, MF2 (M = Zn, Cd, Hg), were investigated via coupled cluster singles, doubles, and perturbative triples, CCSD(T), including core correlation, with a series of correlation consistent basis sets ranging in size from triple-zeta through quintuple-zeta quality, which were then extrapolated to the complete basis set (CBS) limit using a variety of extrapolation procedures. The explicitly correlated coupled cluster method, CCSD(T)-F12b, was employed as well. Although exhibiting quite different convergence behavior, the F12b method yielded the CBS limit estimates closely matching more computationally expensive conventional CBS extrapolations. The convergence with respect to basis set size was examined for the contributions entering into composite vibrational spectroscopy, including those from higher-order correlation accounted for through the CCSDT(Q) level of theory, second-order spin-orbit coupling effects assessed within four-component and two-component relativistic formalisms, and vibrational anharmonicity evaluated via a perturbative treatment. Overall, the composite results are in excellent agreement with available experimental values, except for the CdF2 bond-stretching frequencies compared to spectral assignments proposed in a matrix isolation infrared and Raman study of cadmium difluoride vapor species [Loewenschuss et al., J. Chem. Phys. 50, 2502 (1969); Givan and Loewenschuss, J. Chem. Phys. 72, 3809 (1980)]. These assignments are called into question in the light of the composite results.

We present a first-principles study of the static and dynamic aspects of the strong Jahn–Teller (JT) and pseudo-JT (PJT) effects in niobium tetrafluoride, NbF4, in the manifold of its electronic ground state, 2E, and its first excited state, 2T2. The complex topography of the full-dimensional multi-sheeted adiabatic JT/PJT surfaces is analyzed computationally at the complete-active-space self-consistent-field (CASSCF) and multireference second-order perturbation levels of electronic structure theory, providing a detailed characterization of minima, saddle points, and minimum-energy conical intersection points. The calculations reveal that the tetrahedral (Td) configuration of NbF4 undergoes strong JT distortions along the bending mode of e symmetry, yielding tetragonal molecular structures of D2d symmetry with Td → D2d stabilization energies of about 2000 cm−1 in the X̃2E state and about 6400 cm−1 in the Ã2T2 state. In addition, there exists strong X̃2E−Ã2T2 PJT coupling via the bending mode of t2 symmetry, which becomes important near the crossing seam of the X̃2E and Ã2T2 potential energy surfaces. A five-state five-mode JT/PJT vibronic-coupling Hamiltonian is constructed in terms of symmetry-invariant polynomial expansions of the X̃2E and Ã2T2 diabatic potential energy surfaces in the e and t2 bending coordinates. The parameters of the Hamiltonian are determined by a least-squares fit of its eigenvalues to the CASSCF ab initio data. The vibronic spectra and the time evolution of adiabatic electronic population probabilities are computed with the multi-configuration time-dependent Hartree method. The complexity of the spectra reflects the effects of the exceptionally strong E × e and T2 × e JT couplings and (E + T2) × (e + t2) PJT coupling. The time evolution of the populations of the adiabatic electronic states after the initial preparation of the Ã2T2 state reveals the femtosecond nonadiabatic dynamics through a multidimensional seam of conical intersection. These results represent the first study of the static and dynamical JT/PJT effects in the X̃2E and Ã2T2 electronic states of NbF4.