Stereomutation dynamics in hydrogen peroxide

Fehrensen, Benjamin; Luckhaus, David; Qüack, Martin

doi:10.1016/j.chemphys.2007.06.012

Cited by 59 publications

(86 citation statements)

References 100 publications

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“…Therefore, HOOH, H 2 NÀNH 2 and its homologues are among the simplest representatives. [180,181] In the vibrational ground state, HOOH converts between left-and right-handed helices on a timescale of 3 ps (full oscillation period) [182] after being localized in one of the helicities. Its dimer features two equivalent hydrogen bonds and is presumably centrosymmetric, that is, it involves monomers of opposite helicity.…”

Section: Intramolecular Counterparts Of Chirality Inductionmentioning

confidence: 99%

Chirality Recognition between Neutral Molecules in the Gas Phase

2008

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Noncovalent interactions are particularly intriguing when they involve chiral molecules, because the interactions change in a subtle way upon replacing one of the partners by its mirror image. The resulting phenomena involving chirality recognition are relevant in the biosphere, in organic synthesis, and in polymer design. They may be classified according to the permanent or transient chirality of the interacting partners, leading to chirality discrimination, chirality induction, and chirality synchronization processes. For small molecules, high-level quantum chemical calculations for such processes are feasible. To provide reliable connections between theory and experiment, such phenomena are best studied in vacuum isolation at low temperature, using rotational, vibrational, electronic, and photoionization spectroscopy. We review these techniques and the results which have become available in recent years, with special emphasis on dimers of permanently chiral molecules and on the influence of conformational flexibility. Analogies between the microscopic mechanisms and macroscopic phenomena and between intra- and intermolecular cases are drawn.

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Section: Intramolecular Counterparts Of Chirality Inductionmentioning

confidence: 99%

Chirality Recognition between Neutral Molecules in the Gas Phase

2008

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“…] can be seen from Figure 11. The conclusion by Fehrensen et al (2007) is that one has essentially quasiadiabatic above barrier tunneling to very high vibrational energies. A quasiadiabatic channel reaction path hamiltonian (RPH) approach provides a good approximation, indeed, for the full-dimensional quantum dynamics.…”

Section: Figure 11mentioning

confidence: 99%

“…In many such test calculations, the representations of PESs were not global because they were represented only along certain reaction channels (reaction paths). Since the last decade, "exact" quantum mechanical calculations of scattering processes became feasible, mainly between atoms and diatomic molecules (Schatz 1996), as well as photodissociation processes (Schinke 1993) and stereomutation (Fehrensen et al 1999(Fehrensen et al , 2007.…”

Section: A Brief Historymentioning

confidence: 99%

“…Thus, the understanding of its reaction dynamics is of interest for a wide range of questions and a global potential hypersurface of great importance. Here we summarize some Quack and Suhm (1996) and Kuhn et al (1999) main features of the potential constructed by Kuhn et al (1999) and discuss one particular application, the fully six-dimensional stereomutation quantum dynamics, which is the first example of a full-dimensional treatment of this kind of process (Fehrensen et al 1999(Fehrensen et al , 2007. Several analytical potentials were constructed by Kuhn et al (1999) based on a combination of DFT (B3LYP) CASPT2 calculations and further adjustment to experimental (spectroscopic) properties of H 2 O 2 .…”

Section: Potential Surface For Full-dimensional Reaction Dynamics In mentioning

confidence: 99%

“…However, real quantum dynamics for this molecule happens in a space of the six internal degrees of freedom and a full-dimensional potential hypersurface allows for such a quantum dynamics study (Fehrensen et al 1999(Fehrensen et al , 2007, which then also allows us to study the dependence of tunneling dynamics upon the excitation of various nontorsional vibrational modes. This is shown in Figure 11.…”

Section: Figure 11mentioning

confidence: 99%

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Global Analytical Potential Energy Surfaces for High‐resolution Molecular Spectroscopy and Reaction Dynamics

Marquardt¹,

Qüack²

2011

Handbook of High‐resolution Spectroscopy

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Analytical representations of potential energy hypersurfaces for the nuclear motion in polyatomic molecules from ab initio theory and experiment are discussed in a general way. The qualification of potential hypersurface representations from ab initio theory regarding the description of experimental data from rovibrational high-resolution spectroscopy and chemical reaction kinetics is analyzed in more detail for a restricted group of molecules including methane, CH 4 , ammonia, NH 3 , H 2 O 2 , and (HF) 2 . Current methods for the derivation of analytical representations of potential energy surfaces as well as some applications are reviewed.

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Fundamentals of Rotation–Vibration Spectra

Albert

Hollenstein

et al. 2011

Handbook of High‐resolution Spectroscopy

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We provide a survey of fundamental aspects of rotation-vibration spectra. A basic understanding of the concepts is obtained from a detailed discussion of rotation-vibration spectra of diatomic molecules with only one vibrational degree of freedom. This includes approximate and exact separation of rotation and vibration, effective spectroscopic constants, the effects of nuclear spin and statistics, and transition probabilities derived from the form of the electric dipole moment function. The underlying assumptions and accuracy of the determination of molecular structure from spectra are discussed. Polyatomic molecules show many interacting vibrational degrees of freedom. Energy levels and spectra are discussed on the basis of normal coordinates and effective Hamiltonians of interacting levels in Fermi resonance, and in more complex resonance polyads arising from anharmonic potential functions. The resulting time-dependent dynamics of intramolecular energy flow is introduced as well. Effective Hamiltonians for interacting rotation-vibration levels are derived and applied to the practical treatment of complex spectra. Currently available computer programs aiding assignment and analysis are outlined.

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Stereomutation dynamics in hydrogen peroxide

Cited by 59 publications

References 100 publications

Chirality Recognition between Neutral Molecules in the Gas Phase

Chirality Recognition between Neutral Molecules in the Gas Phase

Global Analytical Potential Energy Surfaces for High‐resolution Molecular Spectroscopy and Reaction Dynamics

Fundamentals of Rotation–Vibration Spectra

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