Threshold photoelectron spectroscopy of 9-methyladenine: theory and experiment.

We present a combined experimental and theoretical study of single-photon ionization of 9-methyladenine (9MA) in the gas phase. In addition to tautomerism, several rotamers due to the rotation of the methyl group may exist. Computations show, however, that solely one rotamer contributes because of low population in the molecular beam and/or unfavorable Franck-Condon factors upon ionization. Experimentally, we used VUV radiation available at the DESIRS beamline of the synchrotron radiation facility SOLEIL to record the threshold photoelectron spectrum of this molecule between 8 and 11 eV. This spectrum consists of a well-resolved band assigned mainly to vibronic levels of the D0 cationic state, plus a contribution from the D1 state, and two large bands corresponding to the D1, D2 and D3 electronically excited states. The adiabatic ionization energy of 9MA is measured at 8.097 ± 0.005 eV in close agreement with the computed value using the explicitly correlated coupled cluster approach including core valence, scalar relativistic and zero-point vibrational energy corrections. This work sheds light on the complex pattern of the lowest doublet electronic states of 9MA+. The comparison to canonical adenine reveals that methylation induces further electronic structure complication that may be important to understand the effects of ionizing radiation and the charge distribution in these biological entities at different time scales.

Electronic structure of the [MgO3]+ cation.

Accurate ab initio calculations are performed to investigate the stable isomers of [MgO(3)](+) and its lowest electronic states at both molecular and asymptotic regions. The calculations are done using large basis sets and configuration interaction methods including the complete active space self-consistent field, the internally contracted multi-reference configuration interaction, the standard coupled cluster (RCCSD(T)) approaches and the newly implemented explicitly correlated coupled cluster method (RCCSD(T)-F12). The presence of three stable forms is predicted: a cyclic global minimum c-MgO(3)(+), which is followed by a quasi-linear isomer, l2-MgO(3)(+). A third isomer of C(s) symmetry (l1-MgO(3)(+)) is also found. Moreover, we computed the one-dimensional cuts of the six-dimensional potential energy surfaces of the lowest doublet and quartet electronic states of [MgO(3)](+) along the R(MgO) and R(OO) stretching coordinates covering both the molecular and the asymptotic regions. These curves are used later for discussing the metastability of this cation and to propose plausible mechanisms for the Mg(+) + O(3) atmospherically important ion-molecule reaction and related reactive channels.

Electronic states of MgO: Spectroscopy, predissociation, and cold atomic Mg and O production.

We used multiconfigurational methods and a large basis set to compute the potential energy curves of the valence and valence-Rydberg electronic states of MgO molecule. New bound electronic states are found. Using these highly correlated wave functions, we evaluated their mutual spin-orbit couplings and transition moment integrals. For the bound electronic states of MgO, we deduced an accurate set of spectroscopic constants that agree remarkably well with experimental results. Moreover, our potentials, transition moments, and spin-orbit coupling evolutions are incorporated into Fermi golden rule calculations to deduce the radiative lifetimes of MgO(B (1)Σ(+)) rovibrational levels and the natural lifetimes of MgO(A (1)Π) vibrational levels, where a good agreement is found with experimental values. Finally, we suggest new routes for the production of cold Mg and O atoms and cold MgO molecules.

Spectroscopic and spin-orbit calculations on the SO+ radical cation.

Highly correlated ab initio methods were used in order to generate the potential-energy curves of the SO+ electronic states correlating to S+(4Su)+O(3Pg) and S+(2Du)+O(3Pg). These curves were used for deducing accurate spectroscopic properties for these electronic states. Our calculations predict the existence of a 2Phi state lying close in energy to the well-characterized b 4Sigma- state and several weakly bound quartet and doublet states located in the 6-9 eV internal energy range not identified yet. The spin-orbit integrals between these electronic states were evaluated using these highly correlated wave functions, allowing the discussion of the metastability and the predissociation processes forming S+ +O in their electronic ground states. Multistep spin-orbit-induced predissociation pathways are suggested. More specifically, the experimentally determined dissociative potential-energy curve [H. Bissantz et al., Z. Phys. D 22, 727 (1992)] proposed to explain the rapid SO+(b 4Sigma-, v> or =13)-->S+(4Su)+O(3Pg) reaction is found to coincide with the 2 4Pi potential-energy curve for short internuclear distances and with the repulsive 1 6Pi state for longer internuclear separations.

Theoretical investigation of the SO(2+) dication and the photo-double ionization spectrum of SO.

Highly correlated ab initio methods were used in order to generate the potential energy curves of the electronic states of the SO(2+) dication and of the electronic ground state of the neutral SO molecule. These curves were used to predict the spectroscopic properties of this dication and to perform forward calculations of the double photoionization spectrum of SO. In light of spin-orbit calculations, the metastability of this doubly charged ion is discussed: for instance, the rovibrational levels of the X (1)Sigma(+) and A (3)Sigma(+) states are found to present relatively long lifetimes. In contrast, the other electronic excited states should predissociate to form S(+) and O(+) in their electronic ground states. The simulated spectrum shows structures due to transitions between the v=0 vibrational level of SO (X (3)Sigma(-)) and the vibrational levels below the barrier maximum of 11 of the calculated electronic states. The 2 (1)Sigma(+) electronic state of SO(2+) received further treatment: in addition to vibrational bands due to the below barrier energy levels of this electronic state, at least nine continuum resonances were predicted which are responsible for the special shape of the spectrum in this energy region. This work is predictive in nature and should stimulate future experimental investigations dealing with this dication.