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Glass‐Maujean, M.; Jungen, Ch.; Reichardt, G.; Balzer, Andreas; Schmoranzer, H.; Ehresmann, A.; Haar, I.; Reiß, Philipp

doi:10.1103/physreva.82.062511

Cited by 46 publications

(74 citation statements)

References 38 publications

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“…However, these perturbations may in turn be used to calculate predissociation widths and shifts of the Rydberg series of interest. 23,59 Combining these ideas with the present MQDT approach should lead to an improved accuracy of the theoretical calculations. Their implementation represents a technical rather than a conceptual problem.…”

Section: Vibrational Basis Sets and Molecular Dissociationmentioning

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: Vibrational Basis Sets and Molecular Dissociationmentioning

confidence: 99%

“…22) and are not subject to predissociation nor to strong rotational channel interactions because they have negative electronic parity. 23 The widths of the corresponding lines were $250 kHz, limited solely by the transit time of the molecules through the measurement region.…”

Section: Latest Measurements Of the Ionisation Energies Of Molecumentioning

confidence: 99%

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

et al. 2011

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“…Equation (3) has been used in Refs. [23] and [24] for the purpose of estimating predissociation widths, but in order to map out the details of the resonances and account for partial cross sections the full approach of Refs. [12][13][14][15][16][17] must be implemented.…”

Section: Mqdt: the I + D Approachmentioning

confidence: 99%

Multichannel quantum defect theory of photodissociation in H₂

Mezei

Schneider

Jungen

2015

EPJ Web of Conferences

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Abstract. The predissociation profiles of the R(0), R(1) and R(2) lines of the 3pg , v = 0 absorption transition in H 2 are calculated in a multichannel quantum defect theory approach, implemented on the basis of state-of-the-art potential energy curves (PEC) from the Wolniewicz group. It is shown that the profiles may be very accurately represented by the Fano profile formula although the resonance parameters thus determined do not exactly coincide with the meaning given to them in Fano's original derivation. The recent high-resolution spectrum of the same transitions taken with the SOLEIL synchrotron is well reproduced by the calculations.

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“…The influence of core excitation on the decay dynamics of Rydberg states has been reported for a number of simple diatomic molecules, including H 2 [21], BH [11][12][13][14]22] and NO [2,[23][24][25][26][27][28]. Recently, GlassMaujean et al measured the absolute cross-sections for competing fluorescence, dissociation and ionisation decay channels in H 2 which, together with a multichannel quantum-defect theory analysis, enabled a full comparison between the three decay processes for several quantum states [21]. In a series of detailed spectroscopic investigations of the Rydberg states of BH, Grant and co-workers investigated the influence of vibrational excitation on the autoionisation lifetime.…”

Section: Introductionmentioning

confidence: 99%

“…the quantum mechanical interferences between the nonradiative decay channels, which form the basis of these control methods [11][12][13][14][15][16][17][18][19][20]. The influence of core excitation on the decay dynamics of Rydberg states has been reported for a number of simple diatomic molecules, including H 2 [21], BH [11][12][13][14]22] and NO [2,[23][24][25][26][27][28]. Recently, GlassMaujean et al measured the absolute cross-sections for competing fluorescence, dissociation and ionisation decay channels in H 2 which, together with a multichannel quantum-defect theory analysis, enabled a full comparison between the three decay processes for several quantum states [21].…”

Section: Introductionmentioning

confidence: 99%

A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO

et al. 2014

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Double-resonance spectroscopy has been employed to characterise the autoionising and predissociating Rydberg states of NO converging to the υ + = 0 and υ + = 1 levels of the X 1 + ground state of NO + . Below the lowest ionisation limit, we monitor the formation of the N( 2 D) predissociation product and observe a spectrum dominated by the p(N + = 0) series, with smaller contributions from the p(2) and f(2) series. Many of the lineshapes can be fit to a simple Fano line profile. Upon vibrational excitation, a competing autoionisation channel is opened and we monitor the products of both the dissociation and ionisation channels. The υ + = 1 predissociation spectrum appears much more complex than the υ + = 0 predissociation spectrum, with significant contributions from the p(0), f(2), p(2), s (1) and d(1) series. In contrast, the υ + = 1 ionisation spectrum is dominated by the p(0) and f(2) Rydberg series, with much weaker contributions from s(1), d(1) and p(2) series. The lineshapes in the υ + = 1 predissociation and autoionisation spectra are perturbed and cannot be fit to simple Fano line profiles. In some extreme cases, these perturbations result in the complete disappearance of peaks from either the autoionisation or predissociation spectrum.

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Competing decay-channel fluorescence, dissociation, and ionization in superexcited levels ofH2

Cited by 46 publications

References 38 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

Multichannel quantum defect theory of photodissociation in H₂

A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO

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Competing decay-channel fluorescence, dissociation, and ionization in superexcited levels ofH2

Cited by 46 publications

References 38 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

Multichannel quantum defect theory of photodissociation in H2

A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO

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Multichannel quantum defect theory of photodissociation in H₂