High n Rydberg spectroscopy of benzene: Dynamics, ionization energy and rotational constants of the cation

Neuhauser, R. G.; Siglow, Klaus; Neusser, H. J.

doi:10.1063/1.473170

Cited by 114 publications

(85 citation statements)

References 53 publications

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“…The energy is given for H 2 relative to the X (v ¼ 0, N ¼ 0) rovibronic ground state. Dn is the natural linewidth [see eqn (4)]. l (2) X and l (2) EF are the wavelengths needed for a twophoton excitation from the X (0,0) and EF (0,0) states, respectively and l (1) n¼60 is the wavelength needed for a one-photon excitation to a n ¼ 60 Rydberg state.…”

Section: A the X / Ef Intervalmentioning

confidence: 99%

“…In these cases, E i can be determined with an accuracy of about 0.01 cm À1 (300 MHz). [4][5][6] Higher accuracies are in general not possible because of inevitable perturbations of the Rydberg series and systematic errors caused by stray electric fields. 7 MQDT alleviates these limitations because it enables one to model the positions of Rydberg states with respect to the ionisation thresholds on the basis of a complete description of the channel interactions and parameters determined empirically or ab initio.…”

Section: Introductionmentioning

confidence: 99%

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Towards measuring the ionisation and dissociation energies of molecular hydrogen with sub-MHz accuracy

et al. 2011

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The most precise determination of the ionisation and dissociation energies of molecular hydrogen H 2 was carried out recently by measuring three intervals independently: the X / EF interval, the EF / n ¼ 54p interval, and the electron binding energy of the n ¼ 54p Rydberg state. The values of the ionisation and dissociation energies obtained for H 2 , and for HD and D 2 in similar measurements, are in agreement with the results of the latest ab initio calculations [Piszczatowski et al., J. Chem. Theory Comput., 2009, 5, 3039; Pachucki and Komasa, Phys. Chem. Chem. Phys., 2010, 12, 9188] within the combined uncertainty limit of 30 MHz (0.001 cm À1 ). We report on a new determination of the electron binding energies of H 2 Rydberg states with principal quantum numbers in the range n ¼ 51-64 with a precision of better than 100 kHz using a combination of millimetre-wave spectroscopy and multichannel quantumdefect theory (MQDT). The positions of 33 np (S ¼ 0) Rydberg states of ortho-H 2 relative to the position of the reference 51d (Rydberg state have been determined with a precision and accuracy of 50 kHz. By analysing these positions using MQDT, the electron binding energy of the reference state could be determined to be 42.3009108(14) cm À1 , which represents an improvement by a factor of $7 over the previous value obtained by Osterwalder et al. [J. Chem. Phys., 2004, 121, 11810]. Because the electron binding energy of the high-n Rydberg states will ultimately be the limiting factor in our method of determining the ionisation and dissociation energies of molecular hydrogen, this result opens up the possibility of carrying out a new determination of these quantities. By evaluating several schemes for the new measurement, the precision limit is estimated to be 50-100 kHz, approaching the fundamental limit for theoretical values of $10 kHz imposed by the current uncertainty of the proton-to-electron mass ratio.

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Section: A the X / Ef Intervalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Towards measuring the ionisation and dissociation energies of molecular hydrogen with sub-MHz accuracy

et al. 2011

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“…By using narrow-bandwidth, near-Fourier-transform-limited pulsed dye lasers to drive resonant multiphoton-ionization processes through selected rovibronic intermediate levels, Neusser and coworkers could overcome the problem of spectral congestion and access long-lived nonpenetrating Rydberg states of large molecules which could be resolved up to n ≈ 100 (Neuhauser et al 1997, Siglow et al 1999, Siglow and Neusser 2000. Fig.…”

Section: Rydberg-series Extrapolation and Threshold Ionizationmentioning

confidence: 99%

“…22b and are fully resolved. The same method was used to determine the rovibrational energy level structure of benzene, benzonitrile, and benzene-rare gas complexes (Neuhauser et al 1997, Siglow et al 1999, Siglow and Neusser 2000.…”

Section: Rydberg-series Extrapolation and Threshold Ionizationmentioning

confidence: 99%

“…The first approach culminated in spectrometers capable of an energy resolution better than 1 meV (Öhrwall and Baltzer 1999). The second approach led successively to (i) the development of threshold photoelectron spectroscopy , Guyon et al 1976, which exploited tunable light sources and the ability to by-pass the measurement of electron kinetic energies by restricting the detection to electrons of near-zero kinetic energies; (ii) the development of resonance-enhanced-multiphoton-ionization photoelectron spectroscopy (REMPI-photoelectron spec-HRS071 High-resolution photoelectron spectroscopy troscopy) which enabled one (1) to use narrow-bandwidth laser radiation and multiphoton excitation through selected intermediate levels, and (2) to ionize energetically close to the thresholds and detect slow electrons at high-resolution (Wilson et al 1984, Allendorf et al 1989; (iii) the development of zero-kinetic-energy photoelectron spectroscopy (ZEKE photoelectron spectroscopy) (Müller-Dethlefs et al 1984) and its variant of pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron HRS071 High-resolution photoelectron spectroscopy 5 spectroscopy (Reiser et al 1988) and of mass-analyzed threshold ionization (MATI) spectroscopy (Zhu and Johnson 1991) which enabled one to resolve the rotational structure in the photoelectron spectra of a wide range of molecules; (iv) the exploitation of velocity-map imaging to enhance the energy resolution in the detection of slow electrons (Osterwalder et al (2004a)); and (v) the development of methods combining the techniques of Rydberg-series extrapolation and threshold ionization, such as cross-correlation-ionization-energy spectroscopy (CRIES) (Neuhauser et al 1997), Rydberg-stateresolved threshold-ionization (RSR-TI) spectroscopy ) and millimeter-wave Rydberg spectroscopy combined with multichannel quantum-defect theory (Osterwalder et al 2004b) to resolve fine-and hyperfine-structure intervals in molecular cations.…”

Section: Introductionmentioning

confidence: 99%

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High‐resolution Photoelectron Spectroscopy

Merkt

Willitsch

Hollenstein

2011

Handbook of High‐resolution Spectroscopy

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The evolution of photoelectron spectroscopy of neutral molecules in the gas phase, from its first applications in the early 1960s to the present day, is reviewed with emphasis on the description of methods that have contributed to the improvement of resolution. In the early days, photoelectron spectroscopy was very successfully used to study the electronic structure of molecules. As the resolution improved, the emphasis gradually shifted to studies of the structure and dynamics of molecular cations. Current methods enable one to fully resolve the rotational structure in the photoelectron spectra of polyatomic molecules and even to measure the fine and hyperfine structures of positively charged atoms and small molecules. Several of the methods providing high resolution make use of the long lifetimes and electric‐field‐ionization properties of high Rydberg states and give access to detailed information on molecular ionization channels and molecular photoionization.

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High‐Resolution Spectroscopy and Intramolecular Dynamics

Neusser¹,

Neuhauser²

1997

Advances in Chemical Physics

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High n Rydberg spectroscopy of benzene: Dynamics, ionization energy and rotational constants of the cation

Cited by 114 publications

References 53 publications

Towards measuring the ionisation and dissociation energies of molecular hydrogen with sub-MHz accuracy

Towards measuring the ionisation and dissociation energies of molecular hydrogen with sub-MHz accuracy

High‐resolution Photoelectron Spectroscopy

High‐Resolution Spectroscopy and Intramolecular Dynamics

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