Penning ionization widths by Fano-algebraic diagrammatic construction method.

We present an ab initio theory and computational method for Penning ionization widths. Our method is based on the Fano theory of resonances, algebraic diagrammatic construction (ADC) scheme for many-electron systems, and Stieltjes imaging procedure. It includes an extension of the Fano-ADC scheme [V.

Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics.

We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al.

Beyond structure: ultrafast X-ray absorption spectroscopy as a probe of non-adiabatic wavepacket dynamics.

The excited state non-adiabatic dynamics of polyatomic molecules, leading to the coupling of structural and electronic dynamics, is a fundamentally important yet challenging problem for both experiment and theory. Ongoing developments in ultrafast extreme vacuum ultraviolet (XUV) and soft X-ray sources present new probes of coupled electronic-structural dynamics because of their novel and desirable characteristics. As one example, inner-shell spectroscopy offers localized, atom-specific probes of evolving electronic structure and bonding (via chemical shifts).

Molecular hydrogen interacts more strongly when rotationally excited at low temperatures leading to faster reactions.

The role of internal molecular degrees of freedom, such as rotation, has scarcely been explored experimentally in low-energy collisions despite their significance to cold and ultracold chemistry. Particularly important to astrochemistry is the case of the most abundant molecule in interstellar space, hydrogen, for which two spin isomers have been detected, one of which exists in its rotational ground state whereas the other is rotationally excited. Here we demonstrate that quantization of molecular rotation plays a key role in cold reaction dynamics, where rotationally excited ortho-hydrogen reacts faster due to a stronger long-range attraction.