marinero_1982

E. E. Marinero, C. T. Rettner and R. N. Zare, “Quantum-state-specific detection of molecular hydrogen by three-photon ionization”, Phys. Rev. Lett. 48, 1323 (1982)

Source record · Catalogue · Review register

DOI: 10.1103/PhysRevLett.48.1323

Source kind: measurement

Recorded technique: (2 + 1) resonance-enhanced multiphoton ionisation of H2 through single rotational levels of E,F 1Sigma_g+, the two photons from anti-Stokes orders of a Raman shifter: a Nd:YAG-pumped rhodamine 6G dye laser (Quanta-Ray, 568.7-577.5 nm) frequency doubled, the doubled light and the residual fundamental focused into an H2 Raman cell (60 cm, 100 psi), all orders focused by an f = 10 cm MgF2 lens (the chamber window) into flowing H2 (15-100 mTorr; to above 1 Torr for the O and S branches), the pairs 3AS + 4AS, 3AS + 3AS and 2AS + 3AS reaching the E,F - X (0,0), (0,1) and (0,2) bands; ions collected on a coaxial electrode (1 MOhm, boxcar); the anti-Stokes energies measured by pyroelectric joulemeters after a Pellin-Broca prism; the sample heated to 295-748 K (pp. 1323-1324).

Materials in structured entries: None recorded.

Dataset quantities: None recorded.

Contents: 0 datasets; 0 formulas.

Curation notes

Phys. Rev. Lett. 48(19), 1323-1326 (10 May 1982) = PDF pages 1-4 (journal page = PDF page + 1322); a scan with a text layer. Identity checked against the first page (VOLUME 48, NUMBER 19, PHYSICAL REVIEW LETTERS, 10 MAY 1982; received 26 February 1982; Marinero, Rettner and Zare, Stanford) on 2026-10-09. The lower half of PDF page 4 is the start of the next Letter in the issue (P. Hannaford and G. W. Series, on level-crossing optogalvanic spectroscopy of 89Y, p. 1326), which the library’s paper.md appends; it is not part of this paper. Numbers read on the rendered pages (pp. 1323-1325) and Table I’s image.

NO DATASET. The paper is a detection method; the numbers it prints are relative signals, others’ values or line positions deduced from others’ tables.

WHAT THE PAPER ESTABLISHES (quoted). (1) The E,F state ‘has a radiative lifetime of 100 +- 20 ns’ (p. 1323, Refs. 9, 10: Kligler and Rhodes 1978; kligler_1980), quoted: held as kligler_1980’s tau_EF_v2 (reproduced from the 1978 Letter); not taken twice. (2) The ion yield in the limit of complete ionisation of the excited molecules (‘expected for I > 10^8 W cm-2’), Eq. (1), i(J’’) = pi alpha E1 E2 N(0, J’’) / (2 h c t_p), with alpha ‘the two-photon absorption cross section’ and ‘a calculated value [12] for alpha of 1.6 x 10^-30 cm4 W-1 (for a measured one-photon laser bandwidth of 0.92 cm-1)’, E1 = 13 uJ, E2 = 49 uJ, N(0, J’’) ~ 2.2 x 10^14 cm^-3, t_p = 2 ns: about 8.8 x 10^6 ions per pulse against 8.4 x 10^6 measured (an ion current of 1.35 x 10^-11 A on Q1) (p. 1324). NOT TAKEN: alpha is a peak coefficient for one laser bandwidth (cm4/W, rate alpha I^2 / hbar omega), not the frequency-integrated two_photon_excitation_cross_section (a conversion needs the line shape), and it is reproduced from Bischel et al. (Ref. 12 = bischel_1979, TC-917), which prints for H2 E,F (v = 2) at 193 nm an estimate of 9 x 10^-33 cm4/W for a 100 cm^-1 line (that record’s notes); scaled inversely with the bandwidth that would be 9.8 x 10^-31 at 0.92 cm^-1, 0.6 of the 1.6 x 10^-30 quoted here, but the (0,0) band at 202 nm is a different transition from the (2,0) band at 193 nm, so this is no check. (3) No three-photon ionisation cross section is printed: the third photon is assumed to saturate the ionisation (above), so the ion signal measures the two-photon rate. (4) Table I (p. 1325, tbl_7a5fdcf34d41): Q-branch ion signals normalised to Q0 at 295, 560 and 748 K, the Boltzmann ratios, and their weighted ratio R_J’’ (Q1 0.98 +- 0.03, Q2 1.14 +- 0.05, Q3 1.07 +- 0.03, Q4 1.07 +- 0.08, Q5 1.39 +- 0.2), the relative two-photon rotational line strengths of the E,F - X (0,0) Q branch for linear polarisation, compared with Eq. (3) (Bray and Hochstrasser) with (mu_S / mu_I)^2 ~ 1, ‘the predominant intermediate state must have Pi rather than Sigma character’, the C 1Pi_u state; the rotational temperatures from Fig. 3, 291 +- 5, 582 +- 19 and 730 +- 24 K against 295, 560 and 748 K. NOT TAKEN: no quantity holds relative rotational line strengths, and they are of interest for diagnostics, not for the gas’s response. (5) Two-photon band ranges, 98 350-99 156 cm^-1 ((0,0)), 94 995-95 261 ((0,1)) and 90 646-91 074 ((0,2)) (p. 1324), and Fig. 2’s Q-line positions, Q3 98 829.31, Q2 98 992.19, Q1 99 101.12, Q0 99 156.76 cm^-1, ‘deduced from the experimental assignments of Dieke’ (Ref. 11, Crosswhite’s edition of Dieke’s tables, 1972). NOT TAKEN: reproduced from tables not in the library; Q0(0,0) would be the T0 of E,F (electronic_state_energy, kind T0), but see the finding.

FINDING (the E,F energies from Dieke’s tables). Q1(0,0) = 99 101.12 cm^-1 here is 8.61 cm^-1 below the EF (0, N = 1) - X (0, N = 1) interval 99 109.731 39(18) cm^-1 of Hannemann et al. 2006 that liu_2009 (TC-575) records in its notes (Table II, (2)); and Q0(0,0) = 99 156.76 is 7.8 cm^-1 below the T0 that the band origins in nist_webbook_2026 (TC-863, Huber and Herzberg) give, E -> B 8961.23 plus B -> X 90 203.35 = 99 164.58 cm^-1. The Dieke-based positions printed here are therefore about 8 cm^-1 low; kligler_1980’s E,F (v = 2) levels come from the same tables. Not resolved here (Dieke’s tables are not in the library).

FURTHER DATA CITED: D. J. Kligler and C. K. Rhodes, Phys. Rev. Lett. 40, 309 (1978), held as kligler_1978b (TC-1043). NOT IN THE LIBRARY: The Hydrogen Molecule Wavelength Tables of Gerhard Dieke, ed. H. M. Crosswhite (Wiley, 1972); R. G. Bray and R. M. Hochstrasser, Mol. Phys. 31, 1199 (1976) (two-photon rotational line strengths); J. B. Halpern, H. Zacharias and R. Wallenstein, J. Mol. Spectrosc. 79, 1 (1980). In the library: kligler_1980 (Ref. 10) and bischel_1979 (Ref. 12).

Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.

Datasets

No datasets are recorded.

Formulas

No formulas are recorded.

Corrections

No dataset errata are recorded in this source record.

Formula corrections, where recorded, appear with their formulas above. Curation notes may also discuss corrections or unresolved interpretation. Consult the review register for the checks and decisions.