HCP CPH ISOMERIZATION: Caught in the Act

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Abstract
▪ Abstract In this overview we discuss the vibrational spectrum of phosphaethyne, HCP, in its electronic ground state, as revealed by complementary experimental and theoretical examinations. The main focus is the evolution of specific spectral patterns from the bottom of the potential well up to excitation energies of approximately 25,000 cm−1, where large-amplitude, isomerization-type motion from H–CP to CP–H is prominent. Distinct structural and dynamical changes, caused by an abrupt transformation from essentially HC bonding to mainly PH bonding, set in around 13,000 cm−1. They reflect saddle-node bifurcations in the classical phase space—a phenomenon well known in the nonlinear dynamics literature—and result in characteristic patterns in the spectrum and the quantum-number dependence of the vibrational fine-structure constants. Two polar opposites are employed to elucidate the spectral patterns: the exact solution of the Schrödinger equation, using an accurate potential energy surface and an effective or resonance Hamiltonian (expressed in a harmonic oscillator basis set and block diagonalized into polyads), which is defined by parameters adjusted to fit either the measured or the calculated vibrational energies. The combination of both approaches—together with classical mechanics and semiclassical analyses—provides a detailed spectroscopic picture of the breaking of one bond and the formation of a new one.