The Stark effect in the v+=1 autoionizing Rydberg states of NO

Goodgame, A L; Dickinson, H.; Mackenzie, Stuart R.; Softley, T. P.

doi:10.1063/1.1450552

Cited by 26 publications

(59 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The off-diagonal matrix elements of between different vibrational levels were treated as parameters that only depended on Á, but not on the l, values except that those were subject to a ÁK ¼ 0 selection rule. It is expected that these matrix elements would in reality show a dependence on l and [20,[27][28][29] or by comparison with the parameters determined for the isoelectronic molecule NO [30]. Off-diagonal elements of the quantum defect matrix were set initially to an arbitrary but small value.…”

Section: Resultsmentioning

confidence: 99%

Multichannel quantum defect theory simulations of the Rydberg spectra of HCO

Brownbill¹,

Softley²

2005

Molecular Physics

View full text Add to dashboard Cite

Multi-channel quantum defect theory (MQDT) is used to simulate the photoionization spectrum of HCO involving autoionizing Rydberg states converging on the v þ 2 ¼ 1, 2 and 3 thresholds. The simulations are compared with experimentally recorded spectra of resonances converging to the (03 1 0) state of HCO þ observed from the photoselected 3p 2 Å (030) K 0 ¼ 0, N 0 ¼ 0 intermediate state, and with spectra converging to the lower thresholds obtained by Mayer and co-workers. Matrix elements off-diagonal in l and v þ 2 are included to account for all channel interactions and autoionization. A reasonable agreement between experiment and theory is obtained by optimization of both the diagonal and off-diagonal elements of the quantum defect matrix, which are found to vary with the vibrational quantum number.

show abstract

Section: Resultsmentioning

confidence: 99%

Multichannel quantum defect theory simulations of the Rydberg spectra of HCO

Brownbill¹,

Softley²

2005

Molecular Physics

View full text Add to dashboard Cite

show abstract

“…The Hund's case (d) quantum defects μ p(0) = 0.703 and μ f(2) = 0.0180 were calculated using the Hund's case (b) quantum defects of Goodgame et al [30]. The Rydberg states are accessed via the υ = 0 or 1 levels of the A 2 E + (3sσ ) state, and the similarity between the A-state and Rydberg state potentials facilitates a strong υ = 0 propensity in vibrational transitions and, therefore, the Rydberg states accessed from υ = 0 or 1 correspond to those converging to the υ + = 0 or 1 ionisation limits, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…To satisfy parity criteria and propensity rules [30,33,34], we expect strong transitions from the s component to np Rydberg series with N + = N , from the d component to np and nf series with N + = N , N ± 2, and weaker transitions from the p component to ns and nd series with N + = N ± 1. Vibrational transitions are controlled by the fact that the overriding Franck-Condon factor is for υ = 0 transitions.…”

Section: Methodsmentioning

confidence: 99%

“…For example, Softley and co-workers studied the effect of external electric fields on low Rydberg states of NO with principal quantum number n < 20 [29,30], and Vrakking and Lee investigated the Stark effect in much higher Rydberg states, where n = 40-120 [31]. In our own group, we have studied the intermediate Rydberg states of NO, with principal quantum number n = 25-35 in static and ramped external fields [32][33][34].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2014

View full text Add to dashboard Cite

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.

show abstract

“…Molecular Rydberg states are highly susceptible to the effects of external fields, and these effects are of importance in a number of new applications of Rydberg states [1], including the deceleration and deflection of Rydberg molecule beams [2][3][4][5][6], and recent experiments involving the scattering of Rydberg molecules at surfaces [7,8]. Previous spectroscopic studies of the Stark effect in molecular Rydberg states, primarily in H 2 [8][9][10], Li 2 [11] H 3 [12] and NO [13][14][15][16], have focused on either autoionising states which lie above the ionisation threshold, or those states that are sufficiently long lived and near to threshold to be detected by field ionisation. The requirement for long-lived character implies that the only states observed are those which are relatively immune to predissociation [16].…”

Section: Introductionmentioning

confidence: 99%

The Stark effect in the predissociating Rydberg states of NO

et al. 2008

View full text Add to dashboard Cite

A spectroscopic study of the Stark effect in the predissociating v þ ¼ 0 Rydberg states of nitric oxide, (n ¼ 13-16) is reported. The states are excited by two-colour excitation via the A 2 AE þ , v ¼ 0, N ¼ 0 state in the presence of a field in the range 0-1125 V cm À1 , and the excitation is observed by using (2 þ 1) REMPI detection of nitrogen ( 2 D) atoms formed by predissociation. The spectra recorded over a range of fields are compared with, and show excellent agreement with, multichannel quantum defect theory (MQDT) simulations of the absorption spectra applied in the bound state formalism of Sakimoto [J. Phys. B. 22, 2727[J. Phys. B. 22, (1989]. The spectroscopy demonstrates the possibility of producing N( 2 D) or O( 3 P) atoms with very narrow centre-of-mass frame speed distributions and arbitrarily selected speed.

show abstract

The Stark effect in the v+=1 autoionizing Rydberg states of NO

Cited by 26 publications

References 48 publications

Multichannel quantum defect theory simulations of the Rydberg spectra of HCO

Multichannel quantum defect theory simulations of the Rydberg spectra of HCO

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

The Stark effect in the predissociating Rydberg states of NO

Contact Info

Product

Resources

About