A simulation of the photoelectron spectrum of pyrazolide Available to Purchase

Building on previous theoretical and spectroscopic studies of the pyrazolyl radical, a new three-state quasidiabatic Hamiltonian is reported which reproduces not only the equilibrium geometries and harmonic frequencies of the nominal $X̃A22$ state and low-lying $ÃB12$ excited state, but also the minimum energy points on the lowest two-state $(X̃A22,ÃB12)$ and three-state $(X̃A22,ÃB12,B̃B22)$ seams of conical intersection. The three-state Hamiltonian includes all terms through second order in both the diagonal and off-diagonal blocks. Its construction is accomplished in two steps. First, a nascent Hamiltonian, centered at the lowest energy two-state conical intersection, is determined using ab initio gradients and derivative couplings. Then, the nascent Hamiltonian is improved by optimizing selected contributions to the second-order coefficients to better reproduce relevant minima and harmonic frequencies. This Hamiltonian is then expressed in a basis tailored to describe the neutral states of interest under the multimode vibronic coupling approximation. The vibronic Hamiltonian is diagonalized to obtain negative ion photoelectron spectra for pyrazolide-$h3$ and the completely deuterated analog pyrazolide-$d3$⁠. The resultant spectra, determined employing vibronic Hamiltonians as large as 500 million terms, compare favorably to recent theoretical and spectroscopic results for pyrazolyl-$d3$ and to spectroscopic results for pyrazolyl-$h3$⁠, for which no reliable simulations had been available.