Spectroscopy and picosecond dynamics of aqueous NO2.

We investigate the formation of aqueous nitrogen dioxide, NO2 formed through femtosecond photolysis of nitrate, NO3⁻ and nitromethane CH3NO2(aq). Common to the experiments is the observation of a strong induced absorption at 1610 ± 10 cm(-1), assigned to the asymmetric stretch vibration in the ground state of NO2. This assignment is substantiated through isotope experiments substituting (14)N by (15)N, experiments at different pH values, and by theoretical calculations and simulations of NO2-D2O clusters.

Vibrational dynamics of deoxyguanosine 5'-monophosphate following UV excitation.

The relaxation dynamics of the DNA nucleotide deoxyguanosine 5'-monophosphate (dGMP) following 266 nm photoexcitation has been studied by transient IR spectroscopy with femtosecond time resolution. The induced dynamics of the amide I (carbonyl) stretch, the asymmetric guanine ring stretch and the phosphate asymmetric stretch are monitored in the region 1000-1800 cm(-1). Excitation and subsequent rapid internal conversion to a "hot" ground state is reflected by depletion of the vibrational ground states of the amide I stretch and guanine ring stretch. However, the vibrational ground state of the phosphate is left unperturbed, indicating the absence of vibrational coupling between the guanine ring system and the phosphate group. The vibrational ground state of the amide I is repopulated in 2.5 ps (±0.2 ps) while it takes 3.7 ps (±0.5 ps) to repopulate the guanine ring vibration. This article discusses two possible relaxation pathways of dGMP, as well as the implications of the weak phosphate dynamics.

The hunt for HCO(aq).

In contrast to its strong presence in gas-phase reactions, the formyl radical, HCO, has never been identified in aqueous solution. Here the photolysis of aqueous formate anions, HCOO(-)(aq), following the excitation of the (n pi*) transition at 200 nm is studied by infrared femtosecond transient absorption spectroscopy with the purpose of identifying the aqueous formyl radical photoproduct, HCO(aq). However, HCO(aq) is not observed. The experiments indicate that HCO(aq) exists for less than one picosecond before it reacts with the surrounding water molecules.

Primary formation dynamics of peroxynitrite following photolysis of nitrate.

The photolysis of nitrate, NO3-, in D2O solution has been investigated by femtosecond infrared spectroscopy. In accordance with previous investigations, we observe that the peroxynitrite ion, ONOO-, is the dominant photochemical product following the excitation of nitrate at 200 nm. Moreover, we are able to identify the cis/trans isomers of peroxynitrite and the dynamics of their formation in solution. We observe that the trans- ONOO- isomer is formed directly and solely from the excited NO3- ion within the first two picoseconds after excitation. Subsequently, about half of the trans-ONOO- isomerizes to cis-ONOO- in 25 ps; thereafter, the ratio between the two isomers remains constant for the 300 ps duration of the experiment. The observed vibrational frequencies of the terminal O=N bonds are at 1515 and 1580 cm(-1) for trans- and cis-peroxynitrite, respectively. The detailed analysis of the infrared bands of cis- and trans-peroxynitrite is facilitated by electronic structure calculations on the conformers in a cluster of 11 D2O molecules and by steady-state infrared spectroscopy of ONOO- in D2O. In addition to the formation of ONOO-, the experiments also reveal a slow approximately 50 ps formation of NO2 following the photolysis of nitrate.

Femtosecond photolysis of aqueous formamide.

In this work, we investigate the primary photodynamics of aqueous formamide. The formamide was photolyzed using 200 nm femtosecond pulses, and formation of products and their relaxation was followed with approximately 300 fs time resolution using probe pulses covering the range from 193 to 700 nm. Following excitation, the majority of formamide molecules (approximately 80%) converts the electronic excitation energy to vibrational excitation, which effectively is dissipated to the solvent through vibrational relaxation in just a few picoseconds. The vibrational relaxation is observed as a distinct modulation of the electronic absorption spectrum of formamide. The relaxation process is modeled by a simple one-dimensional wavepacket calculation. A smaller fraction of the excited formamide molecules dissociates to the CHO and NH2 radical pairs, of which 50% escape recombination. In addition to the electronic excitation of formamide, we also observe a small contribution from one-photon ionization of formamide and two-photon ionization and dissociation of the water solvent.

Electron detachment and relaxation of OH-(aq).

Femtosecond transient absorption spectroscopy is used to study the primary reaction dynamics of photoinduced electron detachment of the hydroxide ion in water, OH- (aq). The electron is detached by excitation of OH- (aq) to the charge-transfer-to-solvent (CTTS) state at 200 nm. The subsequent relaxation processes are probed in the spectral range from 193 to 800 nm with femtosecond time resolution. We determine both the time-dependent quantum yields of OH- (aq), OH(aq), and e-(aq), and we observe a transient spectral signature which is assigned to relaxation of hot (OH-)* ions formed via solvent-assisted conversion of the excited CTTS state to OH-. The primary quantum yield of OH(aq) is 65 +/- 5%, while recombination with e-(aq) reduces the yield to 34% after 5 ps and 12% after 200 ps. The yield of hot (OH-)* ions is 35 +/- 5%. Rotational anisotropy measurements of OH- (aq) and OH(aq) indicate a reorientation time for OH- (aq) of 1.9 ps, while no rotational anisotropy is resolved for the OH(aq) radical within our time resolution of 0.3 ps. This is consistent with the notion that OH(aq) radicals formed after electron detachment are only weakly bound to the hydrogen bond network of water. The assignment of the experimental data is supported by a series of electronic structure calculations of simple complexes of OH- (H(2)O)(n).

Investigation of the primary photodynamics of the aqueous formate anion.

We have investigated the primary photodynamics of the aqueous formate anion using femtosecond transient absorption spectroscopy. The formate anions are excited at 200 nm, and the resulting products are probed in the region 200-650 nm. The ultraviolet part of the transient spectrum compares favorably with that of O-(aq). However, its counter radical, HCO(aq), is not observed. In the visible region hydrated electrons are observed. The electrons are produced from photodetachment of the formate anions and from two-photon ionization of water.

The primary photodynamics of aqueous nitrate: formation of peroxynitrite.

We have examined the photochemical reactions occurring after irradiation at 200 nm of the aqueous nitrate ion, NO3(-)(aq). Using femtosecond transient absorption spectroscopy over the range 194-388 nm, we have characterized the formation and subsequent relaxation of the primary photoproducts of nitrate photolysis. The dominant photoproduct is the cis-isomer of peroxynitrite, which accounts for 48% of the excited state molecules initially produced. A slightly smaller fraction, 44%, of the excited molecules return to the electronic ground state of NO3(-) and relax to the vibrational ground state in 2 ps. The remaining 8% of the molecules initially excited react via the *NO + *O2(-) or the NO- + O2 dissociation channels. Formation of NO2(-) and *NO2 is not observed, suggesting that the previous observations of these species in steady-state photolysis are caused by reactions occurring on a longer time scale.