Photo-induced loss of H2 from H2S, CH4, H2O and SiH4, when and why is it possible

We have explored the possibility of forming H & sdot; and H2 from H2S, CH4, H2O and SiH4 in a series of ab initio calculations. The key finding is that H2S can give rise to direct photolytic ultrafast formation of H2 This finding is in agreement with the available experimental data and is a result of a directed pathway that leads toward H2 formation at easily accessible wavelengths. It arises at the (conical) intersection between the two lowest-lying electronic states. This intersection is a result of the valence orbital interaction of the two hydrogen atoms. This interaction is becoming more favorable as the S-H bonds simultaneously becomes longer. The H-S sigma-sigma* bonding interaction cannot compete with the bond formation that takes place between the hydrogens as two bonds stretch simultaneously. For oxygen this interaction it predominant. The reason is that sulfur has a higher principal quantum number and the interaction with the 1s of hydrogen therefore is less favorable. The excited states that are involved in the H2 formation from H2S could be populated by, for example, a two-photon 400 nm excitation. The other hydrides have a more entangled potential energy landscape close to the Franck-Condon region in the direction of the reaction coordinate that leads to H2 loss and as a result the direct loss of a hydrogen atom is favored. A two-photon excitation could be induced by femtosecond laser pulses that at the same time is proposed as a future platform for sensing the H2S molecules with the backward transient absorption scheme. The implication would be that both sensing and photoinduced H2 formation could be in place at the same time which justifies the use of expensive femtosecond light sources getting "two for the price of one".