Exploring ultrafast H-atom elimination versus photofragmentation pathways in pyrazole following 200 nm excitation.
ABSTRACT The role of ultraviolet photoresistance in many biomolecules (e.g., DNA bases and amino acids) has been extensively researched in recent years. This behavior has largely been attributed to the participation of dissociative (1)πσ* states localized along X-H (X ═ N, O) bonds, which facilitate an efficient means for rapid nonradiative relaxation back to the electronic ground state via conical intersections or ultrafast H-atom elimination. One such species known to exhibit this characteristic photochemistry is the UV chromophore imidazole, a subunit in the biomolecules adenine and histidine. However, the (1)πσ* driven photochemistry of its structural isomer pyrazole has received much less attention, both experimentally and theoretically. Here, we probe the ultrafast excited state dynamics occurring in pyrazole following photoexcitation at 200 nm (6.2 eV) using two experimental methodologies. The first uses time-resolved velocity map ion imaging to investigate the ultrafast H-atom elimination dynamics following direct excitation to the lowest energy (1)πσ* state (1(1)A" ← X(1)A'). These results yield a bimodal distribution of eliminated H-atoms, situated at low and high kinetic energies, the latter of which we attribute to (1)πσ* mediated N-H fission. The time constants extracted for the low and high energy features are ~120 and <50 fs, respectively. We also investigate the role of ring deformation relaxation pathways from the first optically bright (1)ππ* state (2(1)A' ← X(1)A'), by performing time-resolved ion yield measurements. These results are modeled using a (1)ππ* → ring deformation → photofragmentation mechanism (a model based on comparison with theoretical calculations on the structural isomer imidazole) and all photofragments possess appearance time constants of <160 fs. A comparison between time-resolved velocity map ion imaging and time-resolved ion yield measurements suggest that (1)πσ* driven N-H fission gives rise to the dominant kinetic photoproducts, re-enforcing the important role (1)πσ* states have in the excited state dynamics of biological chromophores and related aromatic heterocycles.
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ABSTRACT: Extending the previous work of Lan et al. [J. Chem. Phys., 122, 224315 (2005)], a multi-state potential model for the H atom photodissociation is presented. All three "disappearing coordinates" of the departing H atom have been considered. Ab initio CASSCF computations have been carried out for the linear COH geometry of C(2v) symmetry, and for several COH angles with the OH group in the ring plane and also perpendicular to the ring plane. By keeping the C6H5O fragment frozen in a C(2v)-constrained geometry throughout, we have been able to apply symmetry-based simplifications in the constructions of adiabatic model. This model is able to capture the overall trends of twelve adiabats at both torsional limits for a wide range of COH bend angles.Faraday Discussions 01/2013; 163:73-94. · 3.82 Impact Factor
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ABSTRACT: The heteroaromatic ultraviolet chromophore pyrrole is found as a subunit in a number of important biomolecules: it is present in heme, the non-protein component of hemoglobin, and in the amino acid tryptophan. To date there have been several experimental studies, in both the time- and frequency-domains, which have interrogated the excited state dynamics of pyrrole. In this work, we specifically aim to unravel any differences in the H-atom elimination dynamics from pyrrole across an excitation wavelength range of 250-200 nm, which encompasses: (i) direct excitation to the (formally electric dipole forbidden) 1(1)pisigma* (1A2) state; and (ii) initial photoexcitation to the higher energy 1 pipi* (1B2) state. This is achieved by using a combination of ultrafast time-resolved ion yield and time-resolved velocity map ion imaging techniques in the gas phase. Following direct excitation to 1(1)pisigma* (1A2) at 250 nm, we observe a single time-constant of 126 +/- 28 fs for N-H bond fission. We assign this to tunnelling out of the quasi-bound 3s Rydberg component of the 1(1)pisigma* (1A2) surface in the vertical Franck-Condon region, followed by non-adiabatic coupling through a 1(1)pisigma*/S(0) conical intersection to yield pyrrolyl radicals in their electronic ground state (C4H4N(X)) together with H-atoms. At 238 nm, direct excitation to, and N-H dissociation along, the 1(1)pisigma* (1A2) surface is observed to occur with a time-constant of 46 +/- 22 fs. Upon initial population of the 1pipi* (1B2) state at 200 nm, a rapid 1pipi* (1B2) --> 1(1)pisigma* (1A2) --> N-H fission process takes place within 52 +/- 12 fs. In addition to ultrafast N-H bond cleavage at 200 nm, we also observe the onset of statistical unimolecular H-atom elimination from vibrationally hot S(0) ground state species, formed after the relaxation of excited electronic states, with a time-constant of 1.0 +/- 0.4 ns. Analogous measurements on pyrrole-d1 reveal that these statistical H-atoms are released only through C-H bond cleavage.Faraday Discussions 01/2013; 163:95-116. · 3.82 Impact Factor
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ABSTRACT: Photodissociation dynamics after excitation of the Ã state ν'2 = 4 (umbrella) level of ammonia are investigated using ultrafast time-resolved velocity map ion imaging (TR-VMI). These studies extend upon previous TR-VMI measurements [K. L. Wells, G. Perriam, and V. G. Stavros, J. Chem. Phys. 130, 074308 (2009)], which reported the appearance timescales for ground state NH2(X̃)+H photoproducts, born from non-adiabatic passage through an X̃/Ã state conical intersection (CI) at elongated H-NH2 bond distances. In particular, the present work sheds new light on the formation timescales for electronically excited NH2(Ã)+H species, generated from NH3 parent molecules that avoid the CI and dissociate adiabatically. The results reveal a step-wise dynamical picture for the production of NH2(Ã)+H products, where nascent dissociative flux can become temporarily trapped∕impeded around the upper cone of the CI on the Ã state potential energy surface (PES), while on course towards the adiabatic dissociation asymptote - this behavior contrasts the concerted mechanism previously observed for non-adiabatic dissociation into H-atoms associated with ro-vibrationally "cold" NH2(X̃). Initially, non-planar NH3 molecules (species which have the capacity to yield adiabatic photoproducts) are found to evolve out of the vertical Franck-Condon excitation region and towards the CI region of the Ã state PES with a time-constant of 113 ± 46 fs. Subsequently, transient population encircling the CI then progresses to finally form NH2(Ã)+H photoproducts from the CI region of the Ã state PES with a slower time-constant of 415 ± 25 fs. Non-adiabatic dissociation into ro-vibrationally "hot" NH2(X̃) radicals together with H-atoms is also evidenced to occur via a qualitatively similar process.The Journal of Chemical Physics 07/2013; 139(3):034318. · 3.12 Impact Factor