Molecular isomerization induced by ultrashort infrared pulses. II. Pump-dump isomerization using pairs of time-delayed half-cycle pulses

We investigate population transfer across the barrier in a double-well potential, induced by a pair of time-delayed single-lobe half-cycle pulses. We apply this setup both to a one-dimensional (1D) quartic model potential and to a three-dimensional potential representing HCN-->HNC isomerization. Overall the results for the two systems are similar, although in the 3D system some additional features appear not seen in the 1D case. The generic mechanism of population transfer is the preparation by the pump pulse of a wave packet involving delocalized states above the barrier, followed by the essentially 1D motion of the delocalized part of wave packet across the barrier, and the eventual de-excitation by the dump pulse to localized states in the other well. The correct timing is given by the well-to-well passage time of the wave packet and its recurrence properties, and by the signs of the field lobes which determine the direction and acceleration or deceleration of the wave packet motion. In the 3D system an additional pump-pump-dump mechanism linked to wave packet motion in the reagent well can mediate isomerization. Since the transfer time and the pulse durations are of the same order of magnitude, there is also a marked dependence of the dynamics and the transfer yield on the pulse duration. Our analysis also sheds light on the pronounced carrier envelope phase dependence previously observed for isomerization and molecular dissociation with one-cycle and sub-one-cycle pulses.     

Optical Kerr effect in carbon diselenide

We have measured the optical Kerr susceptibility of liquid carbon diselenide and find its value to be (74 ± 11) × 10^?14 csu, with pump and probe wavelengths of 619 and 579 nm, respectively. This value is approximately three times the Kerr susceptibility of carbon disulfide, and is the largest value reported for a simple liquid. A strong dispersion in Kerr susceptibility is observed as the probe frequency is tuned toward the blue, and is likely due to two-photon near-resonant enhancement from the ¹B₂ state. We also report the visible and ultraviolet absorption spectra and linear refractive index measurements of liquid CSe₂.     

Searching for voids in liquids with optical Kerr effect spectroscopy

It has recently been shown [J. Chem. Phys. 2005, 122, 134506; J. Am. Chem. Soc. 2006, 128, 5119] that liquid tetrahydrofuran has an unusual structure that features voids of significant dimension. Such voids should affect other observable properties of this liquid. Here we present temperature-dependent, optical Kerr effect data for tetrahydrofuran and a number of related liquids (furan, cyclopentane, tetrahydropyran, cyclohexane, diethyl ether, and n-pentane) as well as hexamethylphosphoramide to test whether this technique can be used to reveal the presence of sizable voids in liquids.     

Temperature-dependent optical Kerr effect spectroscopy of aromatic liquids

Ultrafast optical Kerr effect (OKE) spectroscopy has been used to study the temperature-dependent dynamics of five aromatic liquids: benzene, benzene-d(6), hexafluorobenzene, mesitylene, and 1,3,5-trifluorobenzene. The intermediate response time of all of the liquids was found to scale with the collective orientational correlation time, as has been observed for other simple liquids. The spectra of hexafluorobenzene, 1,3,5-trifluorobenzene, and mesitylene are qualitatively different from those of the other liquids and exhibit different behavior with temperature. These spectra allow us to assess the influence of different molecular parameters on the shape of the OKE spectrum. On the basis of these data, we propose a model that links the differences in the OKE spectra to corresponding differences in the local ordering of the liquids.     

Picosecond time-resolved multiplex CARS spectroscopy using optical Kerr gating

We have developed a new spectroscopic system for picosecond time-resolved coherent anti-Stokes Raman scattering (CARS) measurements. Using the optical Kerr gating method in conjunction with a nanosecond laser-based CARS system, a time resolution of 1 ps has been achieved. All-trans retinal in 1-butanol has been measured. The observed time-resolved CARS spectra show changes in the 0–10 ps time range, which are ascribed to the photoisomerization dynamics of all-trans retinal in solution.     

Transition‐state spectroscopy using ultrashort laser pulses

To gain a complete understanding of a chemical reaction, it is necessary to determine the structural changes that occur to the reacting molecules during the reaction. Chemists have long dreamed of being able to determine the molecular structure changes that occur during a chemical reaction, including the structures of transition states (TSs). The use of ultrafast spectroscopy to gain a detailed knowledge of chemical reactions (including their TSs) promises to be a revolutionary way to increase reaction efficiencies and enhance the reaction products, which is difficult to do using conventional methods that are based on trial and error. To confirm the molecular structures of TSs predicted by theoretical analysis, chemists have long desired to directly observe the TSs of chemical reactions. Direct observations have been realized by ultrafast spectroscopy using ultrashort laser pulses. Our group has been able to stably generate visible to near‐infrared sub‐5‐fs laser pulses using a noncollinear optical parametric amplifier (NOPA). We used these sub‐5‐fs pulses to study reaction processes (including their TSs) by detecting structural changes. We determine reaction mechanisms by observing the TSs in a chemical reaction and by performing density‐functional theory calculations. DOI 10.1002/tcr.201000018     

Shape and electrostatic effects in optical Kerr effect spectroscopy of aromatic liquids

We present a detailed, temperature-dependent, optical Kerr effect (OKE) study of pyridine, pyridine-d(5), 2,4,6-trifluoropyridine, 2,4,6-trimethylpyridine, and 1,3,5-tris(trifluoromethyl)benzene. By combining these data with those for other aromatic liquids that we have studied previously (Loughnane, B. J.; Scodinu, A.; Fourkas J. T. J. Phys. Chem. B, 2006, 110, 5708), we are able to assess the relative importance of molecular shape and electrostatic forces in determining the form of the OKE reduced spectral density for such liquids.     

Raman spectroscopy of street samples of cocaine obtained using Kerr gated fluorescence rejection

The first use of Kerr gated fluorescence rejection Raman spectroscopy for the analysis of street samples of cocaine in a fluorescing matrix is reported.     

Infrared double-resonance spectroscopy of bromoform with picosecond pulses

Using independently tunable pump and probe pulses in the infrared, time- and frequency-resolved spectroscopy of vibrationally excited, polyatomic molecules in liquids is demonstrated for the first time. Experimental data are presented for CHBr₃, measuring the population lifetime via excited-state absorption of the CH-stretching mode; for larger probe delay, the non-equilibrium population of intermediate vibrational levels in the relaxation ladder of bromoform is observed.     

Ultrafast optical Kerr effect spectroscopy of water confined in nanopores of the gelatin gel

We report on the investigation of a short-time collective dynamics of water confined in the pores of the gelatin gel, using the femtosecond optical Kerr effect spectroscopy. The ultrafast responses of water molecules obtained in bulk liquid and in three concentrations of gelatin gels are explained theoretically, both in a long time and in a short time regime, taking into account all molecular motions. We prove that the contribution of molecules involved in tetrahedral, strongly H-bonded structures stabilizing the gel network increases with the gel concentration. On the other hand the long-time relaxation of water molecules is significantly slowed down in the gel pores.     

Quadrupolar nuclear magnetic resonance spectroscopy in solids using frequency-swept echoing pulses

The acquisition of ideal powder line shapes remains a recurring challenge in solid-state wideline nuclear magnetic resonance (NMR). Certain species, particularly quadrupolar spins in sites associated with large electric field gradients, are difficult to excite uniformly and with good efficiencies. This paper discusses some of the opportunities that arise upon departing from standard spin-echo excitation approaches and switching to echo sequences that use low-power, frequency-swept radio frequency (rf) pulses instead. The reduced powers demanded by such swept rf fields allow one to excite spins in different crystallites efficiently and with orientation-independent pulse angles, while the large bandwidths of interest that are needed by the measurement can be covered, thanks to the use of broadband frequency sweeps. The fact that the spins' evolution and ensuing dephasing starts at the beginning of such rf manipulation calls for the use of spin-echo sequences; a number of alternatives capable of providing the desired line shapes both in the frequency and in the time domains are introduced and experimentally demonstrated. Sensitivity- and lineshape-wise these experiments are competitive vis-a-vis current implementations of wideline quadrupolar NMR based on hard rf pulses; additional opportunities that may derive from these ideas are also briefly discussed.     

Ultrafast spectroscopy with sub-10 fs deep-ultraviolet pulses

Time-resolved transient absorption spectroscopy with sub-9 fs ultrashort laser pulses in the deep-ultraviolet (DUV) region is reported for the first time. Single 8.7 fs DUV pulses with a spectral range of 255-290 nm are generated by a chirped-pulse four-wave mixing technique for use as pump and probe pulses. Electronic excited state and vibrational dynamics are simultaneously observed for an aqueous solution of thymine over the full spectral range using a 128-channel lock-in detector. Vibrational modes of the electronic ground state and excited states can be observed as well as the decay dynamics of the electronic excited state. Information on the initial phase of the vibrational modes is extracted from the measured difference absorbance trace, which contains oscillatory structures arising from the vibrational modes of the molecule. Along with other techniques such as time-resolved infrared spectroscopy, spectroscopy with sub-9 fs DUV pulses is expected to contribute to a detailed understanding of the photochemical dynamics of biologically significant molecules that absorb in the DUV region such as DNA and amino acids.     

Depolarized light scattering versus optical Kerr effect spectroscopy of supercooled liquids: comparative analysis

Recently, heterodyne-detected optical Kerr effect (HD-OKE) spectroscopy was used to study dynamics of supercooled molecular liquids. The studies revealed an apparently new physical phenomenon that had not been reported before from the related depolarized light scattering (DLS), namely, an intermediate power law (nearly logarithmic decay) of the response functions [H. Cang et al., J. Chem. Phys. 118, 2800 (2003)]. Conceptually, HD-OKE and DLS data reflect optical anisotropy fluctuations mainly due to molecular reorientation dynamics in time and frequency domains, respectively. The above-mentioned effects are revealed in the mesoscopic range less, similar1 GHz ( greater, similar100 ps), where no direct comparison of the techniques was reported. In this Communication, we attempt such a comparison of exemplifying HD-OKE literature data of the glass-forming salol (phenyl salicylate), benzophenone, and liquid-crystal forming 4-cyano-4(')-pentylbiphenyl with DLS data of the same systems that we measured down to ca. 200 MHz by a combined tandem Fabry-Perot interferometer plus tandem-grating-monochromator technique. Generally, we find a satisfactory agreement, albeit in some cases with subtle differences at frequencies greater, similar10 GHz. We conclude that, in the mesoscopic dynamic range, HD-OKE and DLS studies provide consistent and comparable information, and therefore their conclusions must agree. We argue that the intermediate power law of HD-OKE is in essence a manifestation of the excess wing of the corresponding frequency-domain data, known long since from broadband dielectric spectroscopy and anticipated from DLS studies of supercooled liquids.     

Double pulse laser-induced breakdown spectroscopy with femtosecond laser pulses

This paper presents results obtained in a study of collinear geometry double pulse femtosecond LIBS analysis of solids in ambient environment. LIBS signal enhancement of 3–10 fold, accompanied by significant improvement of signal reproducibility, in comparison with the single pulse case, has been found in different samples such as brass, iron, silicon, barium sulfate and aluminum when an optimum temporal separation between the two ablating pulses is used. The influence of the delay between pulses in the LIBS signal intensity was investigated and two intervals of interaction were established. A first transient regime from 0 to 50 ps, in which the LIBS signal increases until reaching a maximum, and a second regime that ranges from 50 to 1000 ps (maximum inter-pulse delay investigated) in which the signal enhancement remains constant. Emissions from both ionized and neutral atoms show the same pattern of enhancement with a clear tendency of lines arising from higher energy emissive states to exhibit higher enhancement factors.     

Emission enhancement using two orthogonal targets in double pulse laser-induced breakdown spectroscopy

The enhancement of emission intensity resulting from the interaction between two laser-induced plasmas on two orthogonal targets was investigated using double pulse laser-induced breakdown spectroscopy (LIBS) at 0.7 Pa, by means of time-resolved spectroscopy and fast photography. The results showed that the interaction between both plasmas improved carbon emission intensity in comparison to a single laser-induced plasma. For all the carbon lines of interest 477.2 nm (CI), 426.7 nm (CII), and 473.4 nm (C₂ Swan band head), the intensity enhancement showed a maximum at a delay between lasers in the range from 2 to 5 μs; moreover it increased with the fluence of the first laser. On the other hand, in the case of C₂ the intensity enhancement reached a maximum at 5 mm from the target; however it decreased with increasing fluence of the second laser. The largest intensity enhancement found was twofold for atomic species and sixfold for molecular species.     

Structural relaxation in the hydrogen-bonding liquids N-methylacetamide and water studied by optical Kerr effect spectroscopy

Structural relaxation in the peptide model N-methylacetamide (NMA) is studied experimentally by ultrafast optical Kerr effect spectroscopy over the normal-liquid temperature range and compared to the relaxation measured in water at room temperature. It is seen that in both hydrogen-bonding liquids, beta relaxation is present, and in each case, it is found that this can be described by the Cole-Cole function. For NMA in this temperature range, the alpha and beta relaxations are each found to have an Arrhenius temperature dependence with indistinguishable activation energies. It is known that the variations on the Debye function, including the Cole-Cole function, are unphysical, and we introduce two general modifications: One allows for the initial rise of the function, determined by the librational frequencies, and the second allows the function to be terminated in the alpha relaxation.     

Ultrafast Optical Kerr Effect of ConjugatedSilver Phenylacetylide Complex Oligomer

Conjugatedpolymerswithlargethird-orderopticalnonlinearityhavebeedfocusedfortheirpromisingpotentialsforadvancedmaterialsapplications'.Recently,investigationsoftransitionmetalwithorganicligandsystemshavebeengreatlyintensifiedduetothedelectronsincorporatedintheconjugatedsystem,whichareexpectedtoellhancethehyperpolarizability.Phenylacetyleneandthemetalphenylacetylidesplayimportantrolesinformationofuniquecoordinatedc-lusters',butitseamsthatthestudyofmetalphenylacetylides,particularlyofthesilverphen…     

Site-selective screening by NMR spectroscopy with labeled amino acid pairs

A new method for site-selective screening by NMR is presented. The core of the new method is the dual amino acid sequence specific labeling technique. Amino acid X is labeled with (13)C and amino acid Y is labeled with (15)N. Provided only one XY pair occurs in the amino acid sequence, only one signal in the 1D carbonyl (13)C spectrum will display a splitting due to the (1)J(C'N) coupling. Using this labeling strategy it is possible to screen selectively for binding to a selected epitope without the need for sequence specific assignments. An HNCO spectrum (1D or 2D) can be used either directly as a screening experiment or indirectly to identify what signals to monitor in a 2D (1)H-(15)N correlation spectrum. Chemical shift perturbations upon addition of a potential ligand are easily detected even for large proteins due to the reduced spectral complexity resulting from the use of a selectively labeled sample. The new technique is demonstrated on the human adipocyte fatty acid binding protein FABP-4. Due to the reduced spectral complexity, the method should be applicable to larger proteins than are conventional methods.     

Step-scan near-infrared Fourier-transform Raman spectroscopy with 100 picosecond laser pulses

Time-resolved Fourier-transform Raman scattering with picosecond excitation is reported for the first time. The resonance Raman spectrum of 9,10-diphenylanthracene in its excited single state was obtained by Raman excitation at 1064 nm with 100 ps pulses, following photoexcitation at 355 nm. The implementation and characterization of time-resolved FT-Raman spectroscopy with a step-scan interferometer is discussed. FT-Raman spectra generated with continuous and mode-locked beams in the continuous-scan mode of the interferometer are compared with step-scan FT-Raman spectra generated with 2 kHz pulses.     

Two-dimensional stimulated resonance Raman spectroscopy of molecules with broadband x-ray pulses

Expressions for the two-dimensional stimulated x-ray Raman spectroscopy (2D-SXRS) signal obtained using attosecond x-ray pulses are derived. The 1D- and 2D-SXRS signals are calculated for trans-N-methyl acetamide (NMA) with broad bandwidth (181 as, 14.2 eV FWHM) pulses tuned to the oxygen and nitrogen K-edges. Crosspeaks in 2D signals reveal electronic Franck-Condon overlaps between valence orbitals and relaxed orbitals in the presence of the core-hole.