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Coherence phenomena arise from interference, or the addition, of wave-like amplitudes with fixed phase differences. Although coherence has been shown to yield transformative ways for improving function, advances have been confined to pristine matter and coherence was considered fragile. However, recent evidence of coherence in chemical and biological systems suggests that the phenomena are robust and can survive in the face of disorder and noise. Here we survey the state of recent discoveries, present viewpoints that suggest that coherence can be used in complex chemical systems, and discuss the role of coherence as a design element in realizing function.

By analogy to the Raman depolarization ratio, vibrational quantum beats in pump-probe experiments depend on the relative pump and probe laser beam polarizations in a way that reflects vibrational symmetry. The polarization signatures differ from those in spontaneous Raman scattering because the order of field-matter interactions is different. Since pump-probe experiments are sensitive to vibrations on excited electronic states, the polarization anisotropy of vibrational quantum beats can also reflect electronic relaxation processes. Diagrammatic treatments, which expand use of the symmetry of the two-photon tensor to treat signal pathways with vibrational and vibronic coherences, are applied to find the polarization anisotropy of vibrational and vibronic quantum beats in pump-probe experiments for different stages of electronic relaxation in square symmetric molecules. Asymmetric vibrational quantum beats can be distinguished from asymmetric vibronic quantum beats by a π phase jump near the center of the electronic spectrum and their disappearance in the impulsive limit. Beyond identification of vibrational symmetry, the vibrational quantum beat anisotropy can be used to determine if components of a doubly degenerate electronic state are unrelaxed, dephased, population exchanged, or completely equilibrated. [ABSTRACT FROM AUTHOR]

Polarized femtosecond pump-probe spectroscopy is used to observe electronic wavepacket motion for vibrational wavepackets centered on a conical intersection. After excitation of a doubly degenerate electronic state in a square symmetric silicon naphthalocyanine molecule, electronic motions cause a ∼100 fs drop in the polarization anisotropy that can be quantitatively predicted from vibrational quantum beat modulations of the pump-probe signal. Vibrational symmetries are determined from the polarization anisotropy of the vibrational quantum beats. The polarization anisotropy of the totally symmetric vibrational quantum beats shows that the electronic wavepackets equilibrate via the conical intersection within ∼200 fs. The relationship used to predict the initial electronic polarization anisotropy decay from the asymmetric vibrational quantum beat amplitudes indicates that the initial width of the vibrational wavepacket determines the initial speed of electronic wavepacket motion. For chemically reactive conical intersections, which can have 1000 times greater stabilization energies than the one observed here, the same theory predicts electronic equilibration within 2 fs. Such electronic movements would be the fastest known chemical processes. [ABSTRACT FROM AUTHOR]

The growth of tungsten nitride carbide (WNxCy) films obtained by atomic layer deposition using triethylboron, tungsten hexafluoride, and ammonia precursors is determined by the density and type of reactive sites. The film properties change as a function of thickness. On silicon dioxide and silicon carbide, growth is initially nonlinear such that the transient regimes are characterized by island formation, as evidenced by a parabolic tungsten growth curve extending to film thicknesses of up to 5 nm. Such films have low densities of ∼4–6 g cm-3 corresponding to only ∼30%–45% of the bulk density of ∼13.1 g cm-3 determined for a WN0.45C0.55 composition. X-ray reflectivity, thermal desorption, and elastic recoil detection spectroscopies reveal surface roughening and compositional and density differences close to the substrate surface. The offset from linear growth in the case of WNxCy films deposited on silicon dioxide is induced by the initial reaction of silanol and siloxane groups with triethylborane resulting in passivating ethylsilyl groups on the surface. A transient regime is not observed for WNxCy growth on hydrogen-terminated silicon with the initial growth being dominated by the reduction of tungsten hexafluoride to tungsten. On silicon nitride a short transient regime is observed relative to the carbide and oxide surfaces attributed to the enhanced binding of the triethylboron precursor. [ABSTRACT FROM AUTHOR]

Six of the 14 unidentified bands in the stimulated emission pumping (SEP) spectrum of HCN are shown to be forbidden transitions to l‘=1 e parity levels of the ground state. The band origins agree with predictions within the error of the anharmonic expansion; the rotational constants, when corrected for rotational-l doubling, agree within experimental error. Rotational-l resonance between l‘=0 and l‘=2 is found in highly excited bending levels, confirming the extrapolation of the rotational-l resonance and doubling constant q2 from microwave and infrared measurements to 17 000 cm-1. The rotational intensity of the l‘=1 bands due to the axis-switching mechanism of Hougen and Watson [Can. J. Phys. 43, 298 (1965)] is shown to be greater than some of the observed allowed rotational transitions to l‘=2 when laser polarization effects are taken into account. A qualitative Franck–Condon analysis of the SEP spectrum provides unusually strong evidence for the axis-switching mechanism. The eight remaining unassigned bands are evidently perturbed and are assigned based on agreement between sums of observed rotational constants and sums of zero-order (unperturbed) rotational constants predicted by the anharmonic expansion, the magnitude of the rotational-l resonance, and the expected Franck–Condon factors. [ABSTRACT FROM AUTHOR]

Information about the unimolecular acetylene (HC 3/4 CH)↔vinylidene (H2C=C:) isomerization on the S0 energy surface has been extracted from vibrationally unassigned high resolution stimulated emission pumping (SEP) spectra of acetylene. The combination of a new pattern recognition scheme, spectral cross correlation (SCC) with complete nuclear permutation-inversion (CNPI) group theory is shown to be a powerful new technique for characterizing bond rearrangement in highly vibrationally excited normally rigid polyatomic molecules. SCC detects isomerization ‘‘resonances’’ which destroy an approximate vibrational symmetry (e.g., the number of cis-bending quanta). The energies (relative to the zero point level of the stablest isomer) and widths of such resonances provide information about the ‘‘energies’’ of isomer rovibrational levels and the isomer-level-specific isomerization rate. Vinylidene isomerization resonances may be distinguished from ordinary acetylene Fermi or Coriolis perturbations by a unique rotational symmetry dependence due to the correlation between acetylene [D∞h(M)] and vinylidene [C2v(M)] levels in the CNPI group G8. An SCC map of the HCCH S0 15 000–15 900 cm-1 energy region above the zero point level was obtained by comparing SEP spectra recorded via S1(A 1Au)33 and 2162 Ka=1 intermediate levels. The predicted rotational symmetry dependence of the SCC was found between 15 410–15 640 cm-1, but the vinylidene resonance line shape was obscured by Franck–Condon interference effects from well known perturbations between the 33 and 2162 SEP intermediate levels. It was therefore not yet possible to determine the height of the isomerization barrier (or even whether a barrier exists) but an upper bound for the vinylidene zero point level of 15 525 cm-1 was inferred from the SCC data. [ABSTRACT FROM AUTHOR]

Adherent thin polymer films have been prepared by sequential electro- deposition of ethyl acrylate (EA) and acrylonitrile (AN) onto nickel. Their composition has been studied by IR spectroscopy and time of flight - secondary ion mass spectrometry. Morphology and thickness have been analyzed by atomic force microscopy and ellipsometry, respectively, and compared to single component films of PEA and PAN. No microphase separation was detected in the mixed PEN PAN films. These show a granular morphology comparable to that of PAN films. The grains contain the two constitutive polymers, as confirmed by the selective thermal degradation of PEA. [ABSTRACT FROM AUTHOR]

The simplest two-dimensional (2D) spectra show how excitation with one (variable) frequency affects the spectrum at all other frequencies, thus revealing the molecular connections between transitions. Femtosecond 2D Fourier transform (2D FT) spectra are more flexible and share some of the remarkable properties of their conceptual parent, 2D FT nuclear magnetic resonance. When 2D FT spectra are experimentally separated into real absorptive and imaginary refractive parts, the time resolution and frequency resolution can both reach the uncertainty limit set for each resonance by the sample itself. Coherent four-level contributions to the signal provide new molecular phase information, such as relative signs of transition dipoles. The nonlinear response can be picked apart by selecting a single coherence pathway (e.g., specifying the relative signs of energy level difference frequencies during different time intervals as in the photon echo). Because molecules are frozen on the femtosecond timescale, femtosecond 2D FT experiments can separate a distribution of instantaneous molecular environments and intramolecular geometries as inhomogeneous broadening. This review provides an introduction to two-dimensional Fourier transform experiments exploiting second- and third-order vibrational and electronic nonlinearities. [ABSTRACT FROM AUTHOR]

A complete (both amplitude and phase) measurement of the femtosecond linear free induction decay on a Raman active dye in solution (IR144 in methanol) is demonstrated. For weak femtosecond pulses passing through a homogeneous material, Beer's Law can be used to predict the spectral amplitude changes, and dispersion relations can be used to calculate the spectral phase change. A modified fast Fourier transform algorithm calculates the phase change by applying dispersion relations to a symmetrical absorption spectrum spanning positive and negative frequencies. A reformulation of the rotating wave approximation in the frequency domain shows that related limits on the accuracy of the rotating wave approximation in nonlinear optics arise from the width of the linear spectrum relative to the center frequency, and not from the excitation pulses. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

With the purpose of developing biosensors, the reliable proof of the biological activity of two new sensor systems was obtained by atomic force microscopy (AFM) in both the imaging and the single-molecule force spectroscopy modes. Antigens or antibodies of pharmacological interest were grafted onto self-assembled monolayers of thiols on gold, and AFM imaging demonstrated that the grafting process produced homogeneous submonolayers of isolated proteins. The analysis of the morphology of the surfaces at the different functionalization steps allowed evaluating the protein grafting density and showed that the recognition of complementary species present in the surrounding solution occurred. Single-molecule force spectroscopy experiments between the sensing surfaces and AFM probes, onto which the complementary species were grafted, enabled a direct and rapid test of the biological activity of the sensors by investigating the interaction occurring at the level of one single ligand-receptor bond. Ellipsometry and surface plasmon resonance allowed further characterization of the sensor surfaces and confirmed that the biological recognition took place. [ABSTRACT FROM AUTHOR]

The article discusses a study that reveals that a reactive polymer can be directly grafted from commercial silicon nitride SPM tips, without an intermediate layer. The conditions can be selected to realize an isolated mushroom regime, with only one single chain accessible at the tip apex, or a brush regime. Those modified tips can be used for biomolecular recognition force spectroscopy.