Multiphoton Ionization State Selection: Vibrational‐Mode and Rotational‐State Control

Anderson, Scott L.

doi:10.1002/9780470141397.ch2

Cited by 58 publications

(16 citation statements)

References 60 publications

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“…Vibrationally excited states of ions can be selectively generated by ionizing through a suitable Rydberg state of the relevant neutral precursor molecule and by taking advantage of diagonal Franck-Condon factors in the photoionization step, as demonstrated in several previous studies (see, e.g., Refs. [22,23] and references therein). In combination with rotational-state selection in the Rydberg state, threshold-photoionization schemes can be devised that allow the generation of cations in well-defined excited rovibrational states.…”

Section: Discussionmentioning

confidence: 99%

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Collisional and radiative effects in the state-selective preparation of translationally cold molecular ions in ion traps

2011

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We give a detailed characterization of a recently developed method to prepare translationally cold, internally state-selected molecular ions in ion traps [X. Tong, A. H. Winney, and S. Willitsch, Phys. Rev. Lett. 105, 143001 (2010)]. The technique relies on the generation of molecular ions in a well-defined rotational-vibrational quantum state using threshold photoionization followed by sympathetic cooling of the translational motion with laser-cooled Ca + ions. We discuss the experimental requirements for the successful generation and sympathetic cooling of state-selected ions, explore the influence of collisional and radiative processes on the population redistribution dynamics, and give an assessment of the scope of the method.

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Section: Discussionmentioning

confidence: 99%

“…Resonance-enhanced multiphoton ionization (REMPI) has been employed to generate molecular cations in selected vibrational levels by taking advantage of near-diagonal Franck-Condon factors in the ionization through vibrationally excited Rydberg states (see, e.g., Refs. [22,23] and references cited therein).…”

Section: Generation Of State-selected Molecular Ionsmentioning

confidence: 99%

Collisional and radiative effects in the state-selective preparation of translationally cold molecular ions in ion traps

2011

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“…The occurrence of this effect at low E cm indicates that the long range charge and dipole-induced-multipole interactions of the colliding pair play a significant role in the dynamics of the exothermic H 2 Understanding of mode specificity in reaction dynamics is of fundamental importance. [1][2][3][4][5][6] However, despite many recent advances, systematic investigations of mode specificity are still relatively rare, largely because of difficulties associated with the preparation of the reactant quantum state and with the control of the translational energy. The recent advances in preparing single rovibrational states of the water cation, H 2 O + , 7, 8 using the newly developed vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) method 9-11 has enabled detailed experimental studies of the influence of the H 2 O + rotational and vibrational modes as well as the translational energy on its reaction with D 2 , leading to the D + H 2 DO + products.…”

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confidence: 99%

Communication: The origin of rotational enhancement effect for the reaction of H2O+ + H2 (D2)

Guo

et al. 2014

The Journal of Chemical Physics

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We have measured the absolute integral cross sections (σ's) for H3O(+) formed by the reaction of rovibrationally selected H2O(+)(X(2)B1; v1 (+)v2 (+)v3 (+) = 000; N(+) K a (+) K c (+) = 000, 111, and 211) ion with H2 at the center-of-mass collision energy (Ecm) range of 0.03-10.00 eV. The σ(000), σ(111), and σ(211) values thus obtained reveal rotational enhancements at low Ecm < 0.50 eV, in agreement with the observation of the previous study of the H2O(+)(X(2)B1) + D2 reaction. This Communication presents important progress concerning the high-level ab initio quantum calculation of the potential energy surface for the H2O(+)(X(2)B1) + H2 (D2) reactions, which has provided valuable insight into the origin of the rotational enhancement effect. Governed by the charge and dipole-induced-multipole interactions, the calculation shows that H2 (D2) approaches the H end of H2O(+)(X(2)B1) in the long range, whereas chemical force in the short range favors the orientation of H2 (D2) toward the O side of H2O(+). The reorientation of H2O(+) reactant ion facilitated by rotational excitation thus promotes the H2O(+) + H2 (D2) reaction along the minimum energy pathway, rendering the observed rotational enhancement effects. The occurrence of this effect at low Ecm indicates that the long range charge and dipole-induced-multipole interactions of the colliding pair play a significant role in the dynamics of the exothermic H2O(+) + H2 (D2) reactions.

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“…The resonance enhanced multiphoton ionization (REMPI) is probably the most appealing technique in terms of combining very high cross section, easy to use, with a fairly high selectivity. Evidently, REMPI spectroscopy is a powerful tool for rovibrational state selection of molecular ions, as has been reviewed by Anderson (1992). The author's group has demonstrated state selection of HBr þ and HCl þ ions over a wide range of rotational quantum numbers (Penno, Holzwarth, & Weitzel, 1998Michel, Korolkov, & Weitzel, 2004;Penno & Weitzel, 2004).…”

Section: Binding Energies At Quantum State Resolution-and Beyondmentioning

confidence: 98%

Bond‐dissociation energies of cations—Pushing the limits to quantum state resolution

Weitzel

2011

Mass Spectrometry Reviews

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Currently available concepts for measuring the bond-dissociation energy of cations D(o) are reviewed. Starting from the traditional approach of directly measuring the threshold energy for the appearance of fragment ions, attention is directed towards indirect measurements, where threshold energies are obtained by extrapolation of, for example, rate constants k(E) or kinetic energy release (KER) data to the threshold of interest. More recent high precision techniques again utilize direct measurements, for example, of the disappearance energy of the parent ion. Most precise data are obtained from quantum state resolved measurements of the dissociation energy, where the threshold energy is bracketed by the existing quantum states above and below the threshold. Ultimately the limits can even be pushed beyond the bracketing limit, by investigating steps on the lineshape of homogeneously broadened single rotational transitions.

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Multiphoton Ionization State Selection: Vibrational‐Mode and Rotational‐State Control

Cited by 58 publications

References 60 publications

Collisional and radiative effects in the state-selective preparation of translationally cold molecular ions in ion traps

Collisional and radiative effects in the state-selective preparation of translationally cold molecular ions in ion traps

Communication: The origin of rotational enhancement effect for the reaction of H2O+ + H2 (D2)

Bond‐dissociation energies of cations—Pushing the limits to quantum state resolution

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