Ultrafast radiationless transition pathways through conical intersections in photo-excited 9H-adenine

Abstract

We performed CASSCF and MRCI calculations for determination of the effective pathways of ultrafast radiationless transitions from the optically allowed ππ* 1La state to the ground state S0 of 9H-adenine. The nπ*, πσ*, and two ππ* states were taken into account as states involved in the radiationless process. Optimized geometry and conical intersections were searched in the full dimensional space for the vibrational degrees of freedom by using the suite of quantum chemistry codes MOLPRO. The MRCI transition energies to excited states are in good agreement with the experimental values. The mechanisms of three competing pathways, two indirect pathways via the πσ* and nπ* states, 1La→πσ*→S0 and 1La→nπ*→ S0, and a direct pathway 1La→S0, were examined on the basis of the structures and energies of conical intersections involved in ultrafast radiationless transitions from 1La to S0. Any conical intersection between the πσ* and nπ* states was not found. This suggests that the two indirect pathways are independent of each other. The ππ* 1La-πσ* conical intersection lies higher than the ππ* 1La state at the Franck-Condon geometry by 0.19 eV according to the present MRCI calculation, which is consistent with the experimental observation that a new channel is open at the excess energy of 0.2 eV above the band origin of the ππ* 1La state. It is concluded that relaxation from the ππ* 1La-πσ* conical intersection to S0 occurs mainly through the πσ*-S0 conical intersection. The ππ* 1La-nπ* conical intersection lies higher by 0.1 eV (MRCI value) than the ππ* 1La state at the Franck-Condon geometry. The fast decay component in time-resolved spectra of 9H-adenine is attributed to rapid radiationless transitions to the nπ* state via this conical intersection followed by the transition to S0 via the nπ*-S0 (or ππ* 1La-S0) conical intersection. The ππ* 1La-S0 conical intersection of large out-of-plane distortion has the lowest energy among the conical intersections found in this study. We identified the transition state between the ππ* 1La at the Franck-Condon geometry and the ππ* 1La-S0 conical intersection. The MRCI energy of the transition state on the 1La potential surface is higher by 0.21 eV than the vertical excitation energy. The possibility of strong coupling between the two close-lying states 1La and nπ* indicates that, besides this direct pathway, radiationless transitions to S0 via the ππ* 1La-S0 conical intersection can also occur after rapid relaxations between 1La and nπ*. The analysis of the h-vector for each conical intersection has shown that the active coupling for the πσ* pathway is dominated by the out-of-plane normal mode ν10, while the active coupling for the nπ* pathway is distributed among many normal modes. Control of the branching ratio of the two indirect pathways can be achieved by selective excitation of single vibronic levels involving active coupling modes such as the mode ν10.

QM/MM Nonadiabatic Decay Dynamics of 9H‐Adenine in Aqueous Solution

“…[36] These studies (as well as previous ones and OM2/MRCI) agree on some general qualitative features, for example, the presence of three closely spaced excited states around 5 eV (np*, pp* L a , and pp* L b ), the existence of several competing nonradiative decay channels, and the type of distorted geometries at the corresponding conical intersections, especially for the low-energy 6 S 1 and 2 E species. However, there are significant differences in the computed energies and consequently also in the favored decay mechanisms.…”

On the Participation of Photoinduced N–H Bond Fission in Aqueous Adenine at 266 and 220 nm: A Combined Ultrafast Transient Electronic and Vibrational Absorption Spectroscopy Study

“…The biologically relevant 9H tautomer of Ade (Scheme 1, blue) has received considerable theoretical attention. 9,[12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] A number of conical intersections can potentially facilitate repopulation of S0 from the initially excited 1 ππ* state(s), depending on the initial excitation energy. There has been some debate regarding the dominant pathway for re-accessing S0 after UV excitation in 9H-Ade, although the general consensus is that out-ofplane ring distortion at either the C2 or C6 sites (see Scheme 1) leads to conical intersections which facilitate ultrafast (and near barrierless) internal conversion (IC) back to S0; we note for completeness that recent work suggests direct 1 ππ* → S0 IC is likely to be the dominant process, 9,21,26,31 rather than a sequential 1 ππ* → 1 nπ* → S0 process.…”

Absorption spectroscopy of adenine, 9-methyladenine, and 2-aminopurine in helium nanodroplets

“…The general consent is that the decay dynamics are governed by a number of conical intersections involving the electronic ground state and the lower electronically excited 1 the ground state that is reached along a barrierless path involving a ring-puckering coordinate of the six-membered ring (out-of-plane rotation of the C 2 -N 3 bond). 5,[27][28][29][30][31] Other channels that have attracted considerable attention involve conical intersections with repulsive 1 ps* states along the N 9 -H and N 10 -H coordinates. [32][33][34][70][71][72] These channels, however, only open up at wavelengths shorter than 233 nm 71 and would thus a priori not be expected to be involved in the decay of the 1 np* and 1 L b (pp*) levels studied here.…”

“…3,[18][19][20][21][22][23][24] These results strongly suggest that several channels are of importance for describing electronic relaxation in excited adenine. Indeed, theoretical calculations indicate that various conical intersections are present within the manifold of the electronic ground state S 0 and the lower-lying electronically excited np*, 1 L b (pp*), and 1 L a (pp*) states, 5,[25][26][27][28][29][30][31] while at slightly higher energies also conical intersections with repulsive ps* states come into play. [31][32][33][34] It is clear that the decay dynamics will critically depend on the accessibility of these conical intersections and thus on the excitation energy.…”