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

Biggs, Jason D.; Zhang, Yu; Healion, Daniel; Mukamel, Shaul

doi:10.1063/1.4706899

Cited by 73 publications

(79 citation statements)

References 76 publications

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“…Because this MCTDHF treatment includes a rigorous description of all the ionization continua that constitute principal mechanisms for loss of population to other channels, these calculations provide strong evidence that such experiments will be entirely feasible. The resulting wave packet of the ground state combined with excited Σ and ∆ states could be probed in a similar Raman process near the oxygen K-edge and simulated in a further all-electrons active calculation using MCTDHF to provide a diatomic molecule benchmark of the 1D-SXRS experiment recently proposed [2] for polyatomics. The success of these calculations with 15 active electrons demonstrates the potential for the MCTDHF method for electrons to find general utility similar to that of the MCTDH method [46][47][48] for nuclear dynamics on coupled Born-Oppenheimer potential energy surfaces.…”

Section: Discussionmentioning

confidence: 99%

“…A second X-ray Raman pulse probes the fate of the initial valence excitation, again in a site-specific way. Higher dimensional versions of this idea, in particular 2D-SXRS with three broadband X-ray pulses, have also been explored [2]. These ideas have a distinct advantage over proposals for nonlinear spectroscopy, like the extension of optical four-wave mixing to the X-ray regime [7] or the original suggestion for coherent X-ray Raman spectroscopy [8], in that they do not involve phase matching between different X-ray pulses.…”

Section: Introductionmentioning

confidence: 99%

“…The transitions may however be driven by pulses with parallel polarization in a gas of unoriented molecules. The pulse duration is chosen to be 1.31 fs, somewhat longer than those in the original SXRS proposal [2]. We have not made a systematic study of the pulse parameters.…”

Section: Stimulated Resonant Raman Transitions Near the Nitrogen mentioning

confidence: 99%

“…One experimental possibility that has received considerable attention is that proposed by Biggs et al [2], stimulated X-ray Raman spectroscopy with broad band pulses. The simplest version of this idea, called 1D-SXRS, begins with an X-ray pulse having a duration of the order of 100 attoseconds.…”

Section: Introductionmentioning

confidence: 99%

“…Recent proposals for using nonlinear X-ray spectroscopy to study electronic dynamics in molecules involve the creation of coherent linear combinations of valence states using autoionizing, core excited states as intermediates [1][2][3]. This mechanism permits site specificity; the initial valence excitation is localized on the atomic center supporting the core excitation, and its subsequent evolution across the molecule may be probed by core transitions on other centers.…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast population transfer to excited valence levels of a molecule driven by x-ray pulses

Haxton

McCurdy

2014

Phys. Rev. A

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First-principles quantum mechanical calculations of an intense-field ultrafast two-color core hole stimulated Raman process in nitric oxide are presented. They employ the Multiconfiguration TimeDependent Hartree-Fock (MCTDHF) method with all 15 electrons active. These calculations demonstrate a robust excitation localized on an atom through a core-electron stimulated Raman transition, the first step in proposed stimulated X-ray Raman spectroscopy experiments. A total population transfer of approximately 41% into valence excited states and 30% ionization is obtained via two concurrent 1.31fs pulses of maximum intensity 0.5 and 3 ×10 17 W cm −2 . It is found that both resonant and nonresonant (via the continuum) Raman transitions contribute. All aspects of these calculations except for AC stark shifts are converged with a modest basis of 11 orbitals, demonstrating the efficiency of MCTDHF for the treatment of nonperturbative electronic dynamics in molecules.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Stimulated Resonant Raman Transitions Near the Nitrogen mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ultrafast population transfer to excited valence levels of a molecule driven by x-ray pulses

Haxton

McCurdy

2014

Phys. Rev. A

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Using Ambient Ion Beams to Write Nanostructured Patterns for Surface Enhanced Raman Spectroscopy

Baird

Bag

et al. 2014

Angewandte Chemie

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Electrolytic spray deposition was used to pattern surfaces with 2D metallic nanostructures. Spots that contain silver nanoparticles (AgNP) were created by landing solvated silver ions at desired locations using electrically floated masks to focus the metal ions to an area as little as 20 mm in diameter. The AgNPs formed are unprotected and their aggregates can be used for surface-enhanced Raman spectroscopy (SERS). The morphology and SERS activity of the NP structures were controlled by the surface coverage of landed silver ions. The NP structures created could be used as substrates onto which SERS samples were deposited or prepared directly on top of predeposited samples of interest. The evenly distributed hot spots in the micron-sized aggregates had an average SERS enhancement factor of 10 8 . The surfaces showed SERS activity when using lasers of different wavelengths (532, 633, and 785 nm) and were stable in air.Metallic nanoparticles have attractive properties in catalysis, photonics, and chemical sensing. [1] Raman spectroscopy is a powerful nondestructive technique, [2] the sensitivity of which can be significantly improved through surfaceenhanced or tip-enhanced methods. [3] The enhancement arises from the proximity of the analytes to intense localized fields created by nanoscale objects. [4] The capability to modify, coat, and pattern surfaces with nanostructures is important for SERS and also for a wider range of nanomaterials applications. [5] Conventionally, modified surfaces are constructed by delivering intact nanoparticles to target locations through dropcasting or spin coating. [6] However, the difficulty in positioning discrete particles with control over orientation, position, and degree of aggregation means that drop casting of nanoparticles has not been widely used in the highthroughput preparation of SERS substrates. Immobilized and shell-isolated nanosystems [5b, 6c, 7] address these issues, but the necessary vacuum preparation procedures significantly increase the complexity of such approaches.Ion/surface collisions including ion soft-landing have been used to fabricate surface structures under vacuum. [8] Recently an electrolytic spray ionization method [9] has been developed that is capable of generating noble metal ions directly from their solids under ambient conditions as precursors for nanoparticle synthesis. Herein, we report the in situ fabrication of SERS-active spots and micro-scale patterns by landing ionized silver at desired locations where spontaneous cathodic reduction takes place, allowing the creation of nanostructure assemblies.Silver is a widely used SERS material [10] and the plasmon resonance of silver nanostructures is tunable through the visible to mid-infrared regions of the electromagnetic spectrum. [11] Electrolytic spray deposition readily creates spots of approximately 3 mm in diameter composed of silver particles (AgNP) at desired locations, both on top of previously deposited analyte as well as prior to analyte deposition (Figure 1). Both the NP-on-top and ...

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Using Ambient Ion Beams to Write Nanostructured Patterns for Surface Enhanced Raman Spectroscopy

Baird

Bag

et al. 2014

Angew Chem Int Ed

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

Cited by 73 publications

References 76 publications

Ultrafast population transfer to excited valence levels of a molecule driven by x-ray pulses

Ultrafast population transfer to excited valence levels of a molecule driven by x-ray pulses

Using Ambient Ion Beams to Write Nanostructured Patterns for Surface Enhanced Raman Spectroscopy

Using Ambient Ion Beams to Write Nanostructured Patterns for Surface Enhanced Raman Spectroscopy

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