Electron-proton transfer mechanism of excited-state hydrogen transfer in phenol--(NH3)n (n = 3 and 5)

TL;DR

This study investigates the excited-state hydrogen transfer mechanism in phenol--(NH3)n clusters, revealing that electron transfer and proton migration occur independently with different timescales, and how cluster size influences this process.

Contribution

It provides direct experimental evidence of decoupled electron and proton transfer dynamics in phenol--(NH3)n clusters using time-resolved spectroscopy, highlighting size-dependent effects.

Findings

Electron transfer occurs within 3 ps in phenol--(NH3)5.

Proton transfer completes in approximately 20 ps.

Cluster size affects the coupling and dynamics of electron-proton transfer.

Abstract

Excited state hydrogen transfer (ESHT) is responsible to various photochemical processes of aromatics including photoprotection of nuclear basis. Its mechanism is explained by the internal conversion from aromatic $\pi$$\pi$* to $\pi$$\sigma$* states via conical intersection. It means that the electron is transferred to a diffuse Rydberg like $\sigma$* orbital apart from the proton migration. This picture means the electron and the proton are not move together and its dynamics are different in principle. Here, we have applied the picosecond time-resolved near infrared (NIR) and infrared (IR) spectroscopies to the phenol--(NH 3) 5 cluster, the bench mark system of ESHT, and monitored the electron transfer and proton motion independently. The electron transfer monitored by the NIR transition rises within 3 ps while the overall H transfer detected by the IR absorption of NH vibration appears with the lifetime of $\approx$20 ps. It clearly proves that the electron motion and proton migration are decoupled. Such the difference of the time-evolutions between the NIR absorption and the IR transition has not been detected in the cluster with three ammonia molecules. We will report full of our observation together with theoretical calculations of potential energy surfaces of $\pi$$\pi$* and $\pi$$\sigma$* states, and will discuss the ESHT mechanism and its cluster size-dependence between n = 3 and 5. It is suggested that the presence and absence of a barrier in the proton transfer coordinate cause the different dynamics. 2