Isotope selective overtone spectroscopy of CHCl3 by vibrationally assisted dissociation and photofragment ionization

Hippler, Michael; Qüack, Martin

doi:10.1063/1.471457

Cited by 41 publications

(13 citation statements)

References 36 publications

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“…The longer time is a measure of the time-scale for energy¯ow between the 7/2 1 and 7=2 3 ‡ v 6 zero-order states, when the former is prepared. A similar behaviour was observed in other molecules with isolated C-H stretches, such as CHCl 3 [125] and CHF 3 [126]. For example, in CHCl 3 the energy redistribution for the 4 1 state to the CCl 3`u mbrella' vibration is almost a factor of 100 slower than the about 50 fs redistribution time between stretch and bend.…”

Section: Hydrochloro¯uorocarbon Ssupporting

confidence: 66%

Controlling bond cleavage and probing intramolecular dynamics via photodissociation of rovibrationally excited molecules

Bar¹,

Rosenwaks²

2001

International Reviews in Physical Chemistry

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Photodissociation studies of vibrationless ground state molecules pervade diverse areas of chemical physics, while those of rovibrationally excited molecules are expected to have even more impact due to the additional fascinating possibilities they o er and the new horizons they open. Photodissociation of rovibrationally excited species involves a double-resonance scheme in which a photodissociative transition is initiated from an excited rovibrational state that might substantially a ect the intensity and wavelength dependence of the photoabsorption spectrum. In favourable cases, when the energy is disposed in vibrations that are strongly coupled to the reaction coordinate, this pre-excitation might in¯uence photodissociation pathways and lead to selective bond cleavage. In other cases it might in¯uence the branching ratio between di erent fragments by altering the photodissociation dynamics. Moreover, the photodissociation of rovibrationally excited species can serve as a sensitive means for detection of weak vibrational overtone transitions of jet-cooled molecules, and therefore a promising way for revealing speci®c couplings and time evolution of the prepared vibrational states. Experimental studies on di erent polyatomics are used to demonstrate the above aspects and to show how the mechanism of chemical transformations and the nature of rovibrationally excited states are highlighted by photolysis of these pre-excited molecules.

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Section: Hydrochloro¯uorocarbon Ssupporting

confidence: 66%

Controlling bond cleavage and probing intramolecular dynamics via photodissociation of rovibrationally excited molecules

Bar¹,

Rosenwaks²

2001

International Reviews in Physical Chemistry

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“…[41][42][43][44][45][69][70][71][72][73][74] We may say that IVR in NHD 2 is local and leads to level mixing over a small energy range. Despite the fact that some of the states are clearly mixed combination modes, which is the time independent signature of IVR, there is no evidence of a strong, global coupling between NH stretching and bending vibrations; IVR is certainly less strong than in many CHXYZ compounds.…”

Section: A Vibrational Term Values and Discussion Of Mctdh Parametersmentioning

confidence: 99%

Full-dimensional quantum dynamics of vibrationally highly excited NHD2

Marquardt

Sanrey

Gatti

et al. 2010

The Journal of Chemical Physics

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We report on full-dimensional vibrational quantum dynamics of the highly excited ammonia isotopologue NHD(2) using a newly developed potential energy surface and the MCTDH program package. The calculations allow to realistically simulate an infrared laser induced stereomutation reaction at the pyramidal nitrogen atom in the femtosecond time domain. Our results allow for a thorough qualitative and quantitative understanding of infrared photoinduced stereomutation kinetics, the underlying quantum dynamics, and the reaction mechanisms. Comparison is made with a previous, reduced dimensionality study of the same reaction [R. Marquardt, M. Quack, I. Thanopulos, and D. Luckhaus, J. Chem. Phys. 118, 643 (2003)], and it is shown that slight variances of reduced spaces lead to significantly different kinetics. Because the quantum dynamics depends subtly on variances of reduced spaces, reduced dimensionality treatments are not reliable even for qualitative predictions of the stereomutation kinetics. The first direct comparison between the Multiconfigurational Time Dependent Hartree [M. H. Beck, A. Jäckle, G. A. Worth et al., Phys. Rep. 324, 1 (2000)] and Unimolecular Reactions Induced by Monochromatic Infrared Radiation [M. Quack and E. Sutcliffe, QCPE Bulletin 6, 98 (1986)] program packages on a specific, four dimensional quantum dynamical problem allows for their full validation in the present work.

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“…The former BOMEM prototype system at a somewhat lower resolution has a long record of development with supersonic jet techniques at high resolution in our laboratory [19]. ISOS/IRSIMS in addition to wide scanning range achieves high sensitivity in supersonic jets and in addition mass selection as a special feature [80] [81]. Near infrared cwdiode laser cavity ring down supersonic jet spectroscopy, on the other hand, is a new development [82] [83], which performs superbly by three of the four standards (except for ∆ṽ, where it is still quite good, and where we plan improvements in the future).…”

Section: Some Experimental Techniques For High-resolution Infrared Spmentioning

confidence: 99%

Molecular Spectra, Reaction Dynamics, Symmetries and Life

Qüack¹

2003

Chimia

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We provide a short review of the work of the group for molecular kinetics and spectroscopy at the Laboratory for Physical Chemistry of ETH Zürich contributing to our understanding of the fundamental physical-chemical primary processes in chemical reactions. After a brief historical introduction, we present a selection of recent progress and thinking in three areas: 1. Experiments in high resolution molecular spectroscopy leading us from an elucidation and unraveling of molecular infrared spectra to the understanding of the molecular reaction dynamics and fast intramolecular processes from the nanosecond (1 ns = 10 -9 s) to the femtosecond (1 fs = 10 -15 s) and even sub-fs or attosecond (1 as = 10 -18 s) domain. 2. Theory of fundamental symmetries of physics and their violations in molecular spectra and dynamics of chiral molecules with a discussion of possible consequences for the role of chirality in the origin of life. 3. Speculative considerations on the relationship of spectra and dynamics of chiral molecules with the CPT theorem of physics and with the origin of matter and chiral life, and on the relationship of time reversal symmetry violation with the molecular origin of irreversibility and with the possible molecular origin of thought.

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Isotope selective overtone spectroscopy of CHCl3 by vibrationally assisted dissociation and photofragment ionization

Abstract: Resonant enhanced multiphoton dissociation spectroscopy of molecular ions: Technique and application to CH3I+/CD3I+ AIP Conf.

Cited by 41 publications

References 36 publications

Controlling bond cleavage and probing intramolecular dynamics via photodissociation of rovibrationally excited molecules

Controlling bond cleavage and probing intramolecular dynamics via photodissociation of rovibrationally excited molecules

Full-dimensional quantum dynamics of vibrationally highly excited NHD2

Molecular Spectra, Reaction Dynamics, Symmetries and Life

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