Two-Photon Activation of <i>p</i>-Hydroxyphenacyl Phototriggers: Toward Spatially Controlled Release of Diethyl Phosphate and ATP

Houk, Amanda L.; Givens, Richard S.; Elles, Christopher G.

doi:10.1021/acs.jpcb.5b12150

Cited by 22 publications

(27 citation statements)

References 65 publications

(145 reference statements)

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“…The relative cross sections within a spectrum are more precise, because we simultaneously measure the cross section at each energy using the broadband 2PA technique. The primary source of uncertainty in these measurements is the spatial overlap of pump and probe beams; 82 therefore, we make back-to-back measurements under identical conditions in order to facilitate the comparison between compounds. Previously reported cross sections vary by orders of magnitude and have never been measured consistently for the set of all three compounds.…”

Section: A Comparison Of Experimental 1pa and 2pa Spectramentioning

confidence: 99%

“…The lowest band seems to have some vibronic structure, although this is a difficult region of the spectrum to measure experimentally, due to overlapping Raman bands in the pump-probe measurement. 82 Applying the simple three-Gaussian model gives an excitation energy of 3.76 eV with a microscopic cross section of 45 a.u. for the lowest band, and an excitation energy of 4.82 eV with a microscopic cross section of 331 a.u.…”

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confidence: 99%

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Two-photon absorption spectroscopy of trans-stilbene, cis-stilbene, and phenanthrene: Theory and experiment

Wergifosse

Houk

Krylov

et al. 2017

The Journal of Chemical Physics

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Two-photon absorption (2PA) spectroscopy provides complementary, and sometimes more detailed, information about the electronic structure of a molecule relative to one-photon absorption (1PA) spectroscopy. However, our understanding of the 2PA processes is rather limited due to technical difficulties in measuring experimental 2PA spectra and theoretical challenges in computing higher-order molecular properties. This paper examines the 2PA spectroscopy of trans-stilbene, cis-stilbene, and phenanthrene by a combined experimental and theoretical approach. The broadband 2PA spectra of all three compounds are measured under identical conditions in order to facilitate a direct comparison of the absolute 2PA cross sections in the range 3.5-6.0 eV. For comparison, the theoretical 2PA cross sections are computed using the equation-of-motion coupled-cluster method with single and double substitutions. Simulated 2PA spectra based on the calculations reproduce the main features of the experimental spectra in solution, although the quantitative comparison is complicated by a number of uncertainties, including limitations of the theoretical model, vibronic structure, broadening of the experimental spectra, and solvent effects. The systematic comparison of experimental and theoretical spectra for this series of structurally similar compounds provides valuable insight into the nature of 2PA transitions in conjugated molecules. Notably, the orbital character and symmetry-based selection rules provide a foundation for interpreting the features of the experimental 2PA spectra in unprecedented detail.

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Section: A Comparison Of Experimental 1pa and 2pa Spectramentioning

confidence: 99%

mentioning

confidence: 99%

Two-photon absorption spectroscopy of trans-stilbene, cis-stilbene, and phenanthrene: Theory and experiment

Wergifosse

Houk

Krylov

et al. 2017

The Journal of Chemical Physics

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“…Techniques based on two-photon absorption (2PA), for example, provide temporal and spatial control of the optical excitation process, allowing localized fluorescence excitation and chemical activation. These 2PA methods enable biological applications ranging from 3D and super-resolution imaging to photodynamic therapy, optogenetics, and targeted cell deactivation, [1][2][3][4][5][6][7] often at wavelengths that are long enough for deep tissue penetration. Two-photon activation has similarly been used for non-linear optical (NLO) material applications, including microfabrication, nanolithography, 3D optical data storage, ultrafast electro-optic switching, and a variety of novel nanobiophotonics applications.…”

Section: Introductionmentioning

confidence: 99%

Two-photon absorption spectroscopy of stilbene and phenanthrene: Excited-state analysis and comparison with ethylene and toluene

Wergifosse

Elles

Krylov

2017

The Journal of Chemical Physics

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Two-photon absorption (2PA) spectra of several prototypical molecules (ethylene, toluene, trans- and cis-stilbene, and phenanthrene) are computed using the equation-of-motion coupled-cluster method with single and double substitutions. The states giving rise to the largest 2PA cross sections are analyzed in terms of their orbital character and symmetry-based selection rules. The brightest 2PA transitions correspond to Rydberg-like states from fully symmetric irreducible representations. Symmetry selection rules dictate that totally symmetric transitions typically have the largest 2PA cross sections for an orientationally averaged sample when there is no resonance enhancement via one-photon accessible intermediate states. Transition dipole arguments suggest that the strongest transitions also involve the most delocalized orbitals, including Rydberg states, for which the relative transition intensities can be rationalized in terms of atomic selection rules. Analysis of the 2PA transitions provides a foundation for predicting relative 2PA cross sections of conjugated molecules based on simple symmetry and molecular orbital arguments.

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“…Integrating over the time delay between the pump and probe pulses at each probe frequency removes any contribution from dispersive interactions, such as cross-phase modulation, and gives the full Raman response as a frequency-dependent SRS spectrum, A (ω). The amplitude A (ω) is proportional to the differential Raman scattering cross section, , at probe frequency ω − where E p is the energy of the incident Raman pump pulse, L is the path length of the sample, N is the number density of the liquid, n is the index of refraction, ω p is the Raman pump frequency, and f xy represents the intensity-weighted spatial overlap of the pump and probe beams passing through the sample. The overlap factor, f xy , assumes collinear pump and probe beams with Gaussian spatial profiles .…”

Section: Methodsmentioning

confidence: 99%

Absolute Cross Sections of Liquids from Broadband Stimulated Raman Scattering with Femtosecond and Picosecond Pulses

2020

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Broadband stimulated Raman scattering (SRS) is often observed in applications that use nonlinear spectroscopy to probe the composition or dynamics of complex systems. Whether the SRS response is measured intentionally or unintentionally, as a background signal, the relative scattering intensities provide a quantitative measure of the population profile of target molecules. Solvent scattering is a valuable internal reference for determining absolute concentrations in these applications, but accurate cross sections have been reported for only a limited number of transitions in select solvents and were measured using spontaneous Raman scattering with narrowband continuous wave or nanosecond light sources. This work reports the measurement and analysis of absolute Raman scattering cross sections spanning the frequency range of 500–4000 cm–1 for cyclohexane, DMSO, acetonitrile, methanol, water, benzene, and toluene using broadband SRS with femtosecond and picosecond Raman pump pulses at 488 nm. Varying the duration of the Raman pump pulses from ∼80 fs to >1 ps confirms that the cross sections are independent of the spectral bandwidth across the range of ∼250 to <20 cm–1. The cross sections and depolarization ratios measured using broadband SRS agree with the limited number of previously reported values, after accounting for overlapping transitions in the lower-resolution femtosecond and picosecond spectra. The SRS cross sections reported here can be used with confidence as internal reference standards for a wide range of applications, including nonlinear spectroscopy and coherent microscopy measurements using ultrafast lasers.

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Two-Photon Activation of p-Hydroxyphenacyl Phototriggers: Toward Spatially Controlled Release of Diethyl Phosphate and ATP

Cited by 22 publications

References 65 publications

Two-photon absorption spectroscopy of trans-stilbene, cis-stilbene, and phenanthrene: Theory and experiment

Two-photon absorption spectroscopy of trans-stilbene, cis-stilbene, and phenanthrene: Theory and experiment

Two-photon absorption spectroscopy of stilbene and phenanthrene: Excited-state analysis and comparison with ethylene and toluene

Absolute Cross Sections of Liquids from Broadband Stimulated Raman Scattering with Femtosecond and Picosecond Pulses

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