Ultrafast infrared spectroscopy of vibrational CO-stretch up-pumping and relaxation dynamics of W(CO)6

Arrivo, Steven M.; Dougherty, Thomas P.; Grubbs, W. Tandy; Heilweil, Edwin J.

doi:10.1016/0009-2614(95)00124-m

Cited by 114 publications

(112 citation statements)

References 22 publications

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“…Coherent vibrational climbing can be viewed also as a rapid adiabatic passage leading to efficient excitation of the upper vibrational states, with an efficiency that in theory can be close to 100% because of the coherent nature of the interaction. Vibrational climbing has been demonstrated in small molecules, such as W(CO) 6 (3)(4)(5), NO (6), CO adsorbed on a Ru (001) surface (7), Cr(CO) 6 (8), Mo(CO) 6 (5), Fe(CO) 5 (5), and CH 2 N 2 (9). In this article, we report on the demonstration of coherent vibrational climbing in a biological system, carboxyhemoglobin (HbCO).…”

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Coherent vibrational climbing in carboxyhemoglobin

Ventalon

Fraser

Vos

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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We demonstrate vibrational climbing in the CO stretch of carboxyhemoglobin pumped by midinfrared chirped ultrashort pulses. By use of spectrally resolved pump-probe measurements, we directly observed the induced absorption lines caused by excited vibrational populations up to v ‫؍‬ 6. In some cases, we also observed stimulated emission, providing direct evidence of vibrational population inversion. This study provides important spectroscopic parameters on the CO stretch in the strong-field regime, such as transition frequencies and dephasing times up to the v ‫؍‬ 6 to v ‫؍‬ 7 vibrational transition. We measured equally spaced vibrational transitions, in agreement with the energy levels of a Morse potential up to v ‫؍‬ 6. It is interesting that the integral of the differential absorption spectra was observed to deviate far from zero, in contrast to what one would expect from a simple onedimensional Morse model assuming a linear dependence of dipole moment with bond length.T he recent availability of ultrashort and intense midinfrared pulses in a compact setup (1) provides a convenient means for controlling the nuclear motion of molecules (2). With infrared pulses, only vibrational transitions are addressed while the molecule remains in its electronic ground state during the entire interaction. This makes such an approach particularly suited to complex systems such as proteins. Another fascinating possibility opened up by infrared vibrational control is the prospect of exploring the potential energy surface far from the harmonic region up to the transition state of intraprotein reactions.Coherent vibrational climbing consists of exciting a molecular vibration with an ultrashort midinfrared pulse, the broadband spectrum of which encompasses several vibrational transitions of the molecule. Indeed, these transition frequencies become smaller and smaller while climbing the ladder because of the molecular anharmonicity. Therefore, the climbing efficiency can be increased dramatically when using a negatively chirped pulse so that its high-frequency components, resonant with the lower transitions of the ladder, precede its low-frequency components, resonant with the upper transitions of the ladder. Coherent vibrational climbing can be viewed also as a rapid adiabatic passage leading to efficient excitation of the upper vibrational states, with an efficiency that in theory can be close to 100% because of the coherent nature of the interaction. Vibrational climbing has been demonstrated in small molecules, such as W(CO) 6 (3-5), NO (6), CO adsorbed on a Ru (001) surface (7), Cr(CO) 6 (8), Mo(CO) 6 (5), Fe(CO) 5 (5), and CH 2 N 2 (9). In this article, we report on the demonstration of coherent vibrational climbing in a biological system, carboxyhemoglobin (HbCO). This system was chosen rather than carboxymyoglobin, in which different CO-bound configurations result in an inhomogeneous broadening of the absorption line (10). Experimental MethodsThe 800-nm pulses produced by a titanium͞sapphire regenerative amplifier (Hurrican...

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confidence: 99%

Coherent vibrational climbing in carboxyhemoglobin

Ventalon

Fraser

Vos

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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“…These compounds have very strong infrared absorption coefficients, long population and coherence times, and have mostly homogeneous dynamics, and so are often used as model systems in nonlinear IR spectroscopy. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] W(CO) 6 has a single carbonyl absorption band, while RDC has two coupled modes. 3D IR spectra are collected in both the time-and frequency-domains so as to understand the effects of pulse convolution.…”

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confidence: 99%

Fully absorptive 3D IR spectroscopy using a dual mid-infrared pulse shaper

Mukherjee

Skoff

Middleton

et al. 2013

The Journal of Chemical Physics

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This paper presents the implementation of 3D IR spectroscopy by adding a second pump beam to a two-beam 2D IR spectrometer. An independent mid-IR pulse shaper is used for each pump beam, which can be programmed to collect its corresponding dimension in either the frequency or time-domains. Due to the phase matching geometry employed here, absorptive 3D IR spectra are automatically obtained, since all four of the rephasing and non-rephasing signals necessary to generate absorptive spectra are collected simultaneously. Phase cycling is used to isolate the fifthorder from the third-order signals. The method is demonstrated on tungsten hexacarbonyl (W(CO) 6 ) and dicarbonylacetylacetonato rhodium (I), for which the eigenstates are extracted up to the third excited state. Pulse shaping affords a high degree of control over 3D IR experiments by making possible mixed time-and frequency-domain experiments, fast data acquisition and straightforward implementation.

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“…Previous studies of metal-carbonyl compounds have been focused especially on laser-driven CO vibrational ladder climbing. [9][10][11] A particularly interesting example has been the experimental demonstration of ladder climbing up to the v CO = 6 state in carboxyhemoglobin by Joffre and coworkers. 11 For this example, Meier and Heitz have developed a non-reactive gas phase model to simulate the excitation dynamics by using local control theory.…”

Section: Introductionmentioning

confidence: 99%

Carbonyl vibrational wave packet circulation in Mn2(CO)10 driven by ultrashort polarized laser pulses

Abdel-Latif

Kühn

2011

The Journal of Chemical Physics

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The excitation of the degenerate E 1 carbonyl stretching vibrations in dimanganese decacarbonyl is shown to trigger wave packet circulation in the subspace of these two modes. On the time scale of about 5 picoseconds intramolecular anharmonic couplings do not cause appreciable disturbance, even under conditions where the two E 1 modes are excited by up to about two vibrational quanta each. The compactness of the circulating wave packet is shown to depend strongly on the excitation conditions such as pulse duration and field strength. Numerical results for the solution of the seven-dimensional vibrational Schrödinger equation are obtained for a density functional theory based potential energy surface and using the multi-configuration time-dependent Hartree method.

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Ultrafast infrared spectroscopy of vibrational CO-stretch up-pumping and relaxation dynamics of W(CO)6

Cited by 114 publications

References 22 publications

Coherent vibrational climbing in carboxyhemoglobin

Coherent vibrational climbing in carboxyhemoglobin

Fully absorptive 3D IR spectroscopy using a dual mid-infrared pulse shaper

Carbonyl vibrational wave packet circulation in Mn2(CO)10 driven by ultrashort polarized laser pulses

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