Selecting two-photon sequential ionization pathways in H2 through harmonic filtering.

Recent experiments in gas-phase molecules have shown the versatility of using attosecond pulse trains combined with IR femtosecond pulses to track and control excitation and ionization yields on the attosecond timescale. The interplay between electron and nuclear motions drives the light-induced transitions favoring specific reaction paths, so that the time delay between the pulses can be used as the tracking parameter or as a control knob to manipulate the molecular dynamics. Here, we present ab initio simulations on the hydrogen molecule to demonstrate that by filtering the high harmonics in an attosecond pulse train one can quench or enhance specific quantum paths thus dictating the outcome of the reaction. It is then possible to discriminate the dominant sequential processes in two-photon ionization, as for example molecular excitation followed by ionization or the other way around. More interestingly, frequency filters can be employed to steer the one- and two-photon yields to favor electron emission in a specific direction.

Elucidating the 2D magnetic topology of the 'metal-radical' TTTA⋠Cu(hfac)2 system.

The TTTA⋅Cu(hfac)2 polymer (1; in which TTTA = 1,3,5-trithia-2,4,6-triazapentalenyl, and hfac = (1,1,1,5,5,5)-hexafluoroacetylacetonate) is one of the most prominent examples of the rational use of the 'metal-radical' synthetic approach to achieve ferromagnetic interactions. Experimentally, the magnetic topology of 1 could not be fully deciphered. Herein, the first-principles bottom-up procedure was applied to elucidate the nature and strength of the magnetic JAB exchange interactions present in 1. The computed JAB values give rise to a 2D magnetic topology of ferromagnetic dimers (+11.9 cm(-1)) coupled through weaker antiferromagnetic interactions (-3.0 and -3.2 cm(-1)) in two different spatial directions. The hitherto unknown origin of the antiferromagnetic interdimer interactions is thus unveiled. By using the 2D magnetic topology, the agreement between calculated and experimental χT(T) data is extraordinary. In the metal-radical TTTA⋅Cu(hfac)2 compound, the computational model transcends the local dimer cluster model owing to strong interactions between metal centers and organic radicals, thereby creating a de facto biradical. In addition, it is shown that the magnetic topology cannot be inferred from the polymeric [TTTA⋅⋅⋅Cu(hfac)2]n crystal motif, that is, from its chemical coordination pattern. Instead, one should think in terms of magnetic building blocks, namely, the de facto biradicals.