Multiresonant Coherent Multidimensional Spectroscopy

Wright, John

doi:10.1146/annurev-physchem-032210-103551

Cited by 76 publications

(69 citation statements)

References 91 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The information content in both formalisms is equivalent and one can translate the diagrammatic contributions between the two representations. WMEL diagrams are most commonly used to describe Raman scattering spectroscopies [56], as well as mixed IR-VIS spectroscopies [57,58]. The advantage of using the WMEL diagrams is that representation is clearer for the case when a state (like the OD stretch here) splits to a manifold of states (as a result of coupling to the O· · ·O vibration).…”

Section: Introductionmentioning

confidence: 99%

Three-dimensional infrared spectroscopy of isotope-diluted ice Ih

Perakis

Widmer

Hamm

2013

The Journal of Chemical Physics

View full text Add to dashboard Cite

Using three-dimensional infrared (3D-IR) spectroscopy, we investigate the vibrational dynamics of isotope-diluted ice Ih. By probing the OD stretch mode of HOD in H2O, we observe an extremely rapid decay ( 200 fs) of the population from the second vibrational excited state. Quantum simulations based on a two-dimensional Lippincott-Schroeder potential agree nearly quantitatively with the experimental 3D-IR lineshapes and dynamics. The model suggests that energy dissipation is enhanced due to nonadiabatic effects between vibrational states, which arise from strong mode-mixing between the OD stretch mode with lattice degrees of freedom. Furthermore, we compare the simulation results to ab-initio based potentials, in which the hydrogen bond anharmonicity is too small to reproduce the experimental 3D-IR spectra. We thus conclude that the Lippincott-Schroeder potential effectively coalesces many degrees of freedom of the crystal into one intermolecular coordinate. Three-dimensional infrared spectroscopy of isotope-diluted ice IhFivos Perakis, Joanna A. Borek and Peter Hamm Physikalisch-Chemisches Institut, Universität Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland, phamm@pci.uzh.ch (Dated: June 14, 2013) Using three-dimensional infrared (3D-IR) spectroscopy, we investigate the vibrational dynamics of isotope-diluted ice Ih. By probing the OD stretch mode of HOD in H2O, we observe an extremely rapid decay (≈200 fs) of the population from the second vibrational excited state. Quantum simulations based on a two-dimensional Lippincott-Schroeder potential agree nearly quantitatively with the experimental 3D-IR lineshapes and dynamics. The model suggests that energy dissipation is enhanced due to nonadiabatic effects between vibrational states, which arise from strong mode-mixing between the OD stretch mode with lattice degrees of freedom. Furthermore, we compare the simulation results to ab-initio based potentials, in which the hydrogen bond anharmonicity is too small to reproduce the experimental 3D-IR spectra. We thus conclude that the Lippincott-Schroeder potential effectively coalesces many degrees of freedom of the crystal into one intermolecular coordinate.

show abstract

Section: Introductionmentioning

confidence: 99%

Three-dimensional infrared spectroscopy of isotope-diluted ice Ih

Perakis

Widmer

Hamm

2013

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Aufsätze L. J. G. W. van Wilderen und J. Bredenbeck der experimentellen Umsetzung von 2D-IR-Spektroskopie waren bereits Gegenstand einiger ausgezeichneter Verçffentlichungen, Übersichtsartikel [14,15,[17][18][19][20][21][22][23][24][25][26][27] und Bücher. [4,16] 2D-IR-Spektroskopie ist eine Spektroskopie 3.…”

Section: Methodsunclassified

“…Die IR-IR-Raman-Sequenz (Abbildung 2G), welche auch DOVE-FWM-(doubly vibrationally enhanced four wave mixing) oder EVV-( electron-vibration-vibration)2 D-IR-Spektroskopie genannt wird, [27,[102][103][104] ist ebenfalls eine Spektroskopie 3. Ordnung.…”

Section: Dove-oder Evv-2d-ir-spektroskopieunclassified

Von ultraschnellen Strukturbestimmungen bis zum Steuern von Reaktionen: mehrdimensionale gemischte IR/nicht‐IR‐Schwingungsspektroskopie

Wilderen

Bredenbeck

2015

Angewandte Chemie

View full text Add to dashboard Cite

Ultraschnelle, mehrdimensionale Infrarot‐Spektroskopie ist eine leistungsstarke Methode, um Informationen über molekulare Strukturen und deren Dynamik zu erhalten, die mit linearer Spektroskopie nicht oder nur schwer zugänglich sind. IR‐Pulssequenzen mit resonanten oder nichtresonanten UV‐, Vis‐ oder NIR‐Pulsen erweitern den Einsatzbereich der mehrdimensionalen Schwingungsspektroskopie erheblich und schaffen Möglichkeiten, die weit über die eines reinen IR‐Experimentes hinausgehen. Dazu gehört die oberflächenspezifische 2D‐IR‐Spektroskopie, deren Empfindlichkeit die Untersuchung molekularer Monolagen ermöglicht, die ultraschnelle Strukturbestimmung in Nichtgleichgewichtssystemen, die getriggerte Austauschspektroskopie, die es erlaubt, Edukt‐ und Produktbanden miteinander zu korrelieren, Untersuchung des Zusammenspiels von elektronischen und Kernfreiheitsgraden, die Untersuchung von Wechselwirkungen zwischen Raman‐ und IR‐aktiven Moden, Bildgebung mit chemischem Kontrast, subensembleselektive Photochemie und sogar das Steuern von Photoreaktionen durch selektive IR‐Anregung. Im Folgenden stellen wir nützliche gemischte IR/nicht‐IR‐Pulssequenzen vor, diskutieren deren Eigenheiten und veranschaulichen ihr Anwendungspotenzial.

show abstract

“…One general class of techniques utilizes high-order Raman nonlinearities to uncover dynamics ranging from intermolecular motions in liquids to intramolecular charge transfer [4][5][6][7][8][9][10][11]. Two-dimensional (2D) Fourier transform spectroscopies have also impacted the understanding of a variety of processes in condensed phases [12][13][14][15][16][17][18]. The inner workings of photosynthetic complexes and molecular aggregates are now understood to be far more intricate than previously thought [19][20][21][22][23][24][25][26][27][28].…”

Section: Introductionmentioning

confidence: 99%

Uncovering molecular relaxation processes with nonlinear spectroscopies in the deep UV

et al. 2013

View full text Add to dashboard Cite

a b s t r a c tNonlinear laser spectroscopies in the deep UV spectral range are motivated by studies of biological systems and elementary processes in small molecules. This perspective article discusses recent technical advances in this area with a particular emphasis on diffractive optic based approaches to four-wave mixing spectroscopies. Applications to two classes of systems illustrate present experimental capabilities. First, experiments on DNA components at cryogenic temperatures are used to uncover features of excited state potential energy surfaces and vibrational cooling mechanisms. Second, sub-200 fs internal conversion processes and coherent wavepacket motions are investigated in cyclohexadiene and a-terpinene.Finally, we propose new experimental directions that combine methods for producing few-cycle UV laser pulses in noble gases with incoherent detection methods (e.g., photoionization) in experiments with time resolution near a singlefemtosecond. These measurements are motivated by knowledge of extremely fast non-adiabatic dynamics and the resolution of electronic wavepacket motions in molecules.

show abstract

Multiresonant Coherent Multidimensional Spectroscopy

Cited by 76 publications

References 91 publications

Three-dimensional infrared spectroscopy of isotope-diluted ice Ih

Three-dimensional infrared spectroscopy of isotope-diluted ice Ih

Von ultraschnellen Strukturbestimmungen bis zum Steuern von Reaktionen: mehrdimensionale gemischte IR/nicht‐IR‐Schwingungsspektroskopie

Uncovering molecular relaxation processes with nonlinear spectroscopies in the deep UV

Contact Info

Product

Resources

About