Ultrafast photo-excitation dynamics in isolated, neutral water clusters.

Using the efficient nonlinear conversion scheme which was recently developed in our group [M. Beutler, M. Ghotbi, F. Noack, and I. V. Hertel, Opt. Lett. 134, 1491 (2010); M. Ghotbi, M. Beutler, and F. Noack, ibid 35, 3492 (2010)] to provide intense sub-50 fs vacuum ultraviolet laser pulses we have performed the first real time study of ultrafast, photo-induced dynamics in the electronically excited Ã-state of water clusters (H(2)O)(n) and (D(2)O)(n) , n=2-10. Three relevant time scales, 1.8-2.5, 10-30, and 50-150 fs, can be distinguished which-guided by the available theoretical results-are attributed to H (D)-ejection, OH (OD) dissociation, and a nonadiabatic transition through a conical intersection, respectively. While a direct quantitative comparison is only very preliminary, the present results provide a crucial test for future modeling of excited state dynamics in water clusters, and should help to unravel some of the many still unresolved puzzles about water.

Excimer states in microhydrated adenine clusters.

We present femtosecond pump-probe mass and photoelectron spectra for adenine (A) and microhydrated A(m)(H(2)O)(n) clusters. Three distinct relaxation processes of photoexcited electronic states were distinguished: in unhydrated A, relaxation of the optically bright pipi* state occurred via the dark npi* state with respective lifetimes of <0.1 and 1.3 ps. In microhydrated clusters A(H(2)O)(n), relaxation via the npi* state is quenched by a faster relaxation process, probably involving pisigma* states. For the predominantly hydrogen-bonded adenine dimer (A(2)), excited state relaxation is dominated by monomer-like processes. When the adenine dimer is clustered with several water molecules, we observe a nanosecond lifetime from excimer states in pi-stacked clusters. From the electron spectra we estimate adiabatic ionization potentials of 8.32 eV (A), 8.27 eV (A(H(2)O)(1)), 8.19 eV (A(H(2)O)(2)), 8.10 eV (A(H(2)O)(3)), 8.18 eV (A(2)), and 8.0 eV (A(2)(H(2)O)(3-5)).

Ultrafast deactivation processes in aminopyridine clusters: excitation energy dependence and isotope effects.

Fast excited-state relaxation in H-bonded aminopyridine clusters occurs via hydrogen transfer in the excited state. We used femtosecond pump-probe spectroscopy to characterize the excited-state reaction coordinate. Considerable isotope effects for partially deuterated clusters indicate that H-transfer is the rate-limiting step and validate ab initio calculations in the literature. A nonmonotonous dependence on the excitation energy, however, disagrees with the picture of a simple barrier along the reaction coordinate. An aminopyridine dimer serves as a model for Watson-Crick base pairs, where similar reactions have been predicted by theory.

Ultrafast processes in OClO molecules excited by femtosecond laser pulses at 386-409 nm.

Ultrafast dissociation dynamics in OClO molecules is studied, induced by femtosecond laser pulses in the wavelength region from 386 to 409 nm, i.e., within the wide absorption band to the (approximately)A (2)A(2) electronic state. The decay of the initially excited state due to nonadiabatic coupling to the close lying (2)A(1) and (2)B(2) electronic states proceeds with a time constant increasing from 4.6 ps at 386 nm to 30 ps at 408.5 nm. Dissociation of the OClO molecule occurs after internal conversion within about 250 fs. In addition, a minor channel of direct excitation of the (2)A(1) electronic state has been identified, the lifetime of which increases from a few 100 fs at 386 nm to 2.2 ps at 408.5 nm. Simultaneous excitation of two neighboring vibrational bands in the (approximately)A (2)A(2) state leads to a coherent oscillation of the parent ion signal with the frequency difference of both modes.

Relevance of pi sigma* states in the photoinduced processes of adenine, adenine dimer, and adenine-water complexes.

Ab initio calculations and time-resolved photoionization spectroscopy were carried out to characterize the role of the lowest two pi sigma* excited states for the photoinduced processes in the adenine monomer, adenine dimer, and adenine-water clusters. The calculations show--with respect to the monomer--a stabilization of 0.11-0.14 eV for the pi sigma* states in different isomers of adenine dimer and an even bigger stabilization of 0.14-0.36 eV for isomers of adenine-(H2O)1 and adenine-(H2O)3. Hence, the stabilized pi sigma* states should play an important role in the excited-state relaxation of partially or fully solvated adenine. This conclusion is supported by experimental results: In the adenine monomer, strong n pi* state signals are observed. Those signals are reduced in adenine dimer and vanish in water clusters due to the competing relaxation via the pi sigma* states.

Dynamics of photoinduced processes in adenine and thymine base pairs.

The excited-state dynamics of adenine and thymine dimers and the adenine-thymine base pair were investigated by femtosecond pump-probe ionization spectroscopy with excitation wavelengths of 250-272 nm. The base pairs showed a characteristic ultrafast decay of the initially excited pi pi* state to an n pi* state (lifetime tau(pi pi*) approximately 100 fs) followed by a slower decay of the latter with tau(n pi*) approximately 0.9 ps for (adenine)2, tau(n pi*) = 6-9 ps for (thymine)2, and tau(n pi*) approximately 2.4 ps for the adenine-thymine base pair. In the adenine dimer, a competing decay of the pi pi* state via the pi sigma* state greatly suppressed the n pi* state signals. Similarities of the excited-state decay parameters in the isolated bases and the base pairs suggest an intramonomer relaxation mechanism in the base pairs.

Effect of molasses supplementation on the production of lactating dairy cows fed diets based on alfalfa and corn silage.

Adding sugar to the diet has been reported to improve production in dairy cows. In each of 2 trials, 48 lactating Holsteins (8 with ruminal cannulas) were fed covariate diets for 2 wk, blocked by days in milk into 12 groups of 4, and then randomly assigned to diets based on alfalfa silage containing 4 levels of dried molasses (trial 1) or liquid molasses (trial 2). In both studies, production data were collected for 8 wk, ruminal samples were taken in wk 4 and 8, and statistical models were used that included covariate means and block. In trial 1, experimental diets contained 18% CP and 0, 4, 8, or 12% dried molasses with 2.6, 4.2, 5.6, or 7.2% total sugar. With increasing sugar, there was a linear increase in dry matter intake (DMI), and digestibility of dry matter (DM) and organic matter (OM), but no effect on yield of milk or protein. This resulted in linear decreases in fat-corrected milk (FCM)/DMI and milk N/N-intake. There was a linear decrease in urinary N with increasing sugar, and quadratic effects on milk fat content, yield of fat and FCM, and ruminal ammonia. Mean optimum from these quadratic responses was 4.8% total sugar in these diets. In trial 2, experimental diets contained 15.6% crude protein (CP) and 0, 3, 6, or 9% liquid molasses with 2.6, 4.9, 7.4, or 10.0% total sugar, respectively. Again, there were linear declines in FCM/DMI and milk N/N-intake with increasing sugar, but quadratic responses for DMI, yield of milk, protein, and SNF, digestibility of neutral detergent fiber and acid detergent fiber, milk urea, urinary excretion of purine derivatives, and ruminal ammonia. Mean optimum from all quadratic responses in this trial was 6.3% total sugar. An estimate of an overall optimum, based on yield of fat and FCM (trial 1) and yield of milk, protein, and SNF (trial 2), was 5.0% total sugar, equivalent to adding 2.4% sugar to the basal diets. Feeding more than 6% total sugar appeared to depress production.

Theoretical study of the hydrogen atom transfer in the heterodimer indole-ammonia and comparison with experimental results.

Ab initio calculations on the heterodimer C8H6NH...NH3 are carried out for its ground, the excited pisigma*, and the ground cationic electronic states, enabling the description of hydrogen or proton transfer, respectively. Two-dimensional quantum-dynamical computations on the pisigma* potential surface help one to understand the mechanism and the time scale of the hydrogen transfer. Subsequent decay processes are discussed depending on the vibrational excitation of the ammonium constituent. Finally, the theoretical results obtained are used for the interpretation of the time-dependent signals observed in femtosecond pump-probe experiments.

Ultrafast predissociation dynamics of water molecules excited to the electronic C and D states.

Two-photon excitation with femtosecond laser pulses in the spectral range 240-250 nm was used to prepare vapor phase H(2)O and D(2)O in the C (1)B(1) and D (1)A(1) states. Both states are predissociated via the B (1)A(1) state, forming excited OH/OD(A (2)Sigma(+)) as well as ground state OH/OD(X (2)Pi). We used ultrashort infrared probe pulses (1.65-2.42 microm) to control the ratio between these excited and ground state fragments originating from the dissociation process. Time resolved detection of the OH/OD(A (2)Sigma(+)) --> OH/OD(X (2)Pi) fluorescence allows us to monitor the dynamics of the predissociation. For the heterogeneous predissociation out of the C(1)B(1) state life times of (0.5 +/- 0.1) ps and (1.2 +/- 0.1) ps were found for H(2)O and D(2)O, respectively. The purely homogeneous character of the predissociation out of the D (1)A(1) state was monitored.

Absolute extreme ultraviolet yield from femtosecond-laser-excited Xe clusters.

Large Xe clusters (10(5)-10(6) atoms per cluster) have been irradiated with ultrashort (50 fs) and high-intensity ( approximately 2 x 10(18) W/cm(2)) pulses from a Ti:sapphire multi-TW laser at 800 nm wavelength. Scaling and absolute yield measurements of extreme ultraviolet (EUV) emission in a wavelength range between 7 and 15 nm in combination with cluster target characterization have been used for yield optimization. Maximum emission as a function of the backing pressure and a spatial emission anisotropy covering a factor of two at optimized yields is discussed with a simple model of the source geometry and EUV-radiation absorption. Circularly polarized laser light instead of linear polarization results in a factor of 2.5 higher emission in the 11 to 15 nm wavelength range. This indicates the initial influence of optical-field ionization for the interaction parameter range used and contrasts to collisional heating that seems to influence preferentially higher ionization. Absolute emission efficiency at 13.4 nm of up to 0.5% in 2pi sr and 2.2% bandwidth has been obtained.