chang_1978#
R. S. F. Chang and D. W. Setser, “Radiative lifetimes and two-body deactivation rate constants for Ar(3p5, 4p) and Ar(3p5, 4p’) states”, J. Chem. Phys. 69, 3885-3897 (1978)
Source record · Catalogue · Review register
DOI: 10.1063/1.437126
Source kind: measurement
Recorded technique: Time-resolved laser-induced fluorescence in a flowing afterglow: Ar(4s, 3P2) metastables (~5e10 cm-3, from a hollow cathode discharge; 3P0 : 3P2 about 1 : 8) pumped to single 4p, 4p’ levels by a nitrogen-laser-pumped dye laser (< 1 Angstrom, ~5 ns FWHM; Table I’s pump lines 696.5-912.3 nm), one-photon from 1s5; the strongest other line of the level isolated by a 1 m (or 0.3 m) monochromator onto a cooled photomultiplier and a boxcar (1 ns gate; response better than 3 ns). Single exponential decays at 0.5-8 Torr of argon; the zero-pressure intercepts give the radiative lifetimes, the slopes the two-body deactivation by ground-state argon (Eq. 3, k_I = 1/tau_rad + k_Q [Ar]), least squares. Product 4p, 4p’ levels identified in the emission spectra (300 ns gate) and their time profiles fitted with Eq. (6) for the state-to-state k_nn’; the 4s, 4s’ products (VUV) not observed, their sum by difference. Branching ratios from a hollow-cathode lamp (0.1-0.2 Torr) on three calibrated detection systems (550-1100 nm and an interferometer beyond 1000 nm), A = branching ratio / tau_rad.
Materials in structured entries: Ar
Dataset quantities: collisional_quenching_rate_coefficient, radiative_lifetime, transition_probability
Contents: 12 datasets; 0 formulas.
Curation notes#
J. Chem. Phys. 69(9), 3885-3897 (1 November 1978) = PDF pages 2-14 (PDF page 1 is the AIP download cover; journal page = PDF page + 3883). Identity checked on the first page of the article (PDF p. 2: title, authors, Kansas State University, received 4 May 1978, footer J. Chem. Phys. 69(9), 1 Nov. 1978, 3885) on 2026-10-12. Tables II, III and IV checked cell by cell against the table images and the rendered pages (pp. 3889, 3892).
LEVELS. The paper’s Paschen labels with its Racah labels (Tables II-IV, Fig. 1) and NIST’s (src/optmat/data/external/nist_asd/Ar_I_levels.tsv): 1s5, 1s4 = 3s2.3p5.(2P*<3/2>).4s 2[3/2]* J = 2, 1 (93143.76, 93750.60 cm-1); 1s3, 1s2 = (2P*<1/2>).4s 2[1/2]* J = 0, 1 (94553.67, 95399.83); 2p1 = 4p’[1/2]0 = (2P*<1/2>).4p 2[1/2] J = 0 (108722.62); 2p2 = 4p’[1/2]1 = (2P*<1/2>).4p 2[1/2] J = 1 (107496.42); 2p3 = 4p’[3/2]2 = (2P*<1/2>).4p 2[3/2] J = 2 (107289.70); 2p4 = 4p’[3/2]1 = (2P*<1/2>).4p 2[3/2] J = 1 (107131.71); 2p5 = 4p[1/2]0 = (2P*<3/2>).4p 2[1/2] J = 0 (107054.27); 2p6 = 4p[3/2]2 (106237.55); 2p7 = 4p[3/2]1 (106087.26); 2p8 = 4p[5/2]2 (105617.27); 2p9 = 4p[5/2]3 (105462.76); 2p10 = 4p[1/2]1 (104102.10), all (2P*<3/2>).4p 2[K] J. Evidence (script checks): every row’s Paschen label agrees with its printed Racah label; Table IV’s 30 wavelengths (Angstrom, standard air) equal NIST’s level differences within the printed 1 Angstrom, and its g_k, g_i are the levels’ 2J + 1. OEP 8’s two-photon levels are 2p1, 2p5 (J = 0) and 2p6, 2p8 (J = 2): this paper has 2p6 and 2p8 only (‘Due to the Delta J selection rules, the 2p1 and 2p5 levels could not be excited starting from the Ar(3P2) or Ar(3P0) levels’, p. 3887).
TAKEN (radiative_lifetime, collisional_quenching_rate_coefficient and transition_probability, TC-1011; extraction script tools/extract/chang_1978.py): - Table II (p. 3889), ‘Present work’, radiative lifetimes (ns) of 2p2, 2p3, 2p4, 2p6, 2p7, 2p8, 2p9, 2p10, 26.5-42.2 ns, with the printed +- (‘typically +- 1 nsec’, least squares, p. 3889; level not stated) (tau_Ar, primary). - Table III (p. 3889), deactivation by ground-state argon, 10^-11 cm3 atom-1 s-1: the total k_Q of 2p2, 2p3, 2p4, 2p7, 2p8, 2p9, 2p10 with their +- (’+-(10-20)%’, p. 3889) (kq_self, primary); 2p6 ‘<= 1.8’, footnote b, an upper limit from the slope, held as 0 to 1.8 (kq_self_bound, check); the state-to-state k_nn’ one dataset per product level (k_2p4: 2p3 2.2; k_2p6: 2p3 4.1; k_2p7: 2p6 0.8; k_2p8: 2p6 0.8, 2p7 1.6; k_2p9: 2p6 0.2, 2p8 1.7; primary, fits of the product time profiles, no uncertainty stated); k43 = 1.7 and k98 = 0.6, footnote c ‘assigned using detailed balance and k34 or k89’ (k_2p3_db, k_2p8_db, check; script: 1.72 and 0.58 from NIST’s energies at 300 K); the intermultiplet sums to the 4s, 4s’ manifold that are numbers, 2p2 5.3, 2p3 4.7, 2p4 3.9, 2p7 6.1 (footnote e: 5.5 ‘if allowance is made for k76’), 2p10 2.0 (k_4s, check: k_Q minus the k_nn’, derived). Room temperature (the speeds use 300 K, p. 3888; not stated as the gas temperature): no temperature_k. - Table IV (p. 3892), column CS, A_ki (10^6 s-1) of the 26 lines of the eight measured levels, 0.02-33.20 (A_4p_4s, primary): the hollow-cathode branching ratios times 1/tau_rad of Table II (sum A tau = 1 within 0.4 %, script). ‘Typically +-10%’ (p. 3892; mainly the lifetimes’), level not stated. - NOT TAKEN: k_{9,10} ‘> 1.8’ (a lower limit); the intermultiplet ‘<3.0’ (2p8), ‘<3.5’ (2p9) and 0.0 (2p6, whose k_Q is a bound) and the k_nn’ ‘0.0’ of 2p2 and 2p10 (no product seen); sigma (A^2) = k_Q / <v> (derived; script: <v> = 5.64e4 cm/s, the Ar-Ar mean relative speed at 300 K, reproduces every sigma); Table IV’s parenthesised entries for 2p1 (0.994 to 1s2, 6.43e-3 to 1s4) and 2p5 (0.00 to 1s2, 1.00 to 1s4), measured branching ratios, no quantity (declined with wiese_1989’s 100R, TC-1012); the f column (derived from A by footnote a); the other columns of Tables II and IV (other papers’ and Lilly’s values, reproduced); Table I (pump lines); Figs. 3-7 (decay curves and the branching fractions of Table III).
FINDING (asghar_2020, TC-1060). Its dataset lifetime_chang_1978 (Table 1, footnote b) quotes 26.5 +- 0.4, 27.6 +- 0.9, 33.2 +- 0.8, 27.0 +- 1.0, 29.8 +- 0.7, 32.8 +- 0.7, 30.1 +- 0.4 and 42.2 +- 1.0 ns for 2p2-2p4, 2p6-2p10: equal to Table II here, value and uncertainty, level by level. wiese_1989’s Table II column ‘Chang and Setser’ (26.5, 27.6, 33.2, 27.0, 29.8, 32.8, 30.1, 42.2 ns) is also equal.
FINDING (lifetimes against wiese_1989, TC-1012, and NIST, TC-985). wiese_1989’s 1/sum A, from Quadfasel and Helbig’s lifetimes, are 28.39 (2p2), 28.93 (2p3), 30.17 (2p4), 29.04 (2p6), 29.70 (2p7), 31.01 (2p8), 30.21 (2p9) and 39.22 ns (2p10); NIST’s (whose A are wiese_1989’s) 28.38, 28.90, 30.16, 29.07, 29.68, 30.99, 30.30 and 39.26 ns. Chang and Setser / Wiese: 0.933, 0.954, 1.100, 0.930, 1.003, 1.058, 0.996, 1.076, i.e. 4.7, 1.5, 3.8, 2.0, 0.1, 2.6, 0.3 and 3.0 times the printed +- (Wiese’s own A carry +-5-8 %): agreement for 2p7 and 2p9, differences of 5-10 % elsewhere in both directions, not a common scale. sadeghi_2001 (TC-1066) overlaps at 2p6 (28 +- 3 against 27.0 +- 1.0) and 2p8 (29 +- 3 against 32.8 +- 0.7, 1.3 of Sadeghi’s +-); this paper has no 2p1 or 2p5 lifetime (Table II lists only theory and other measurements for them), so Sadeghi’s 24 and 24 ns have no counterpart here.
FINDING (transition probabilities against NIST, TC-985). CS / NIST (Ar_I_lines_nir.tsv) for the 26 lines: 0.89-1.14 for the 13 lines with A >= 7e6 s-1 (2p2-1s5 1.13, 2p6-1s5 1.14, 2p4-1s3 0.89, 2p8-1s4 0.93, 2p10-1s5 0.93), 0.74-1.21 for the 13 weaker ones; the level ratios follow the lifetime ratios above. Independence: the lifetimes and the branching are this paper’s own; wiese_1989 used Chang and Setser’s branching ratios for the 2p8 and 2p10 lines Nick and Helbig did not measure (wiese_1989’s notes), so NIST’s A of those lines share this paper’s branching but not its scale.
FINDING (state-to-state against nguyen_1978, the same argon process at 300 K). In 10^-11 cm3/s, this paper / Nguyen and Sadeghi: k34 2.2 / 2.75, k36 4.1 / 4.4, k43 1.7 (detailed balance) / 2.3, k67 0.8 / 0.41, k68 0.8 / 0.6, k69 0.2 / 0.1, k78 1.6 / 1.43, k89 1.7 / 1.82, k98 0.6 (detailed balance) / 0.68; k79 not observed here, 2.33 there (the note added in proof, p. 3896: ‘possibly because of poor sensitivity’); k_{9,10} ‘> 1.8’ here against 0.51 there, a factor > 3.5 apart; the 2p2 -> 2p3 transfer, 0.0 here, 0.05 there (below this paper’s ~1e-11 limit). The note added in proof quotes Nguyen and Sadeghi’s preprint as k78 = 1.4, k79 = 2.3, k56 = 1.1, k58 = 0.9 (x 10^-11): their published Table II has 14.3, 23.3, 11.3 and 9.5 (x 10^-12), the last rounding to 1.0, not 0.9.
DOUBTS (printed inconsistencies; no taken value affected). Table IV’s CS f of 2p10-1s2 is 0.028, but footnote a’s formula gives 0.0028 from A = 0.14e6 (as WSM’s 0.0049 does from 0.25e6): a misprint by a factor 10 in a column not taken; 2p10-1s5’s 0.134 is 1.7 % above the formula’s 0.1318; every other f agrees within 0.6 % (script). Table II’s Lilly column here (2p2 25.7, 2p9 28.6) differs from wiese_1989’s Table II ‘Theory Lilly’ (25.6, 28.7) by 0.1 ns. sadeghi_2001 (p. 3147) quotes the 2p6 upper limit as ‘a total quenching constant of 0.18 x 10^-10 ... reported previously’, dropping the ‘<=’.
BEARING ON OEP 8 (for scale). Two-body quenching by argon, 10^-11 cm3/s: 2p6 <= 1.8 (sadeghi_2001: 1.3) and 2p8 4.7 +- 0.7, of which 1.7 to 2p9 (sadeghi_2001’s 2.4 is the loss of the 2p8 + 2p9 pair to other states; 2.4 + Nguyen and Sadeghi’s k89 1.82 = 4.2, within this paper’s +-0.7 of 4.7). No three-body term up to 10 Torr; ‘three-body processes will not be important even at 1 atm’ if k3 < 1e-31 cm6/s (p. 3889), an assumption, not a measurement.
DATA CITED, NOT IN THE LIBRARY: J. Z. Klose, J. Opt. Soc. Am. 57, 1242 (1967) (Ar 4p’ lifetimes, delayed coincidence); R. A. Lilly, J. Opt. Soc. Am. 66, 245 (1976) (intermediate-coupling A of Ar and Kr); R. H. Garstang and J. Van Blerkom, J. Opt. Soc. Am. 55, 1054 (1965); J. B. Shumaker and C. H. Popenoe, J. Opt. Soc. Am. 57, 8 (1967); D. A. Landman, Phys. Rev. 173, 33 (1968) (level-crossing lifetimes).
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
chang_1978/tau_Ar#
{
"id": "tau_Ar",
"material": "Ar",
"file": "Ar/chang_1978__tau_Ar.csv",
"table": "tbl_56408e2b767a",
"quantity": "radiative_lifetime",
"unit": "ns",
"abscissa": "label",
"use": "primary",
"parameters": {
"method": "laser-induced fluorescence after one-photon dye-laser excitation from Ar(1s5) in a flowing afterglow, single-exponential decays at 0.5-8 Torr argon, zero-pressure intercept of the decay rate"
},
"uncertainty": {
"column": true,
"level": "not stated"
}
}
Table II (p. 3889), ‘Present work’: the radiative lifetimes of 2p2, 2p3, 2p4, 2p6, 2p7, 2p8, 2p9, 2p10 (Paschen), 26.5-42.2 ns, with the printed +- (least squares, ‘typically +- 1 nsec’, level not stated). wiese_1989’s 1/sum A: 28.39, 28.93, 30.17, 29.04, 29.70, 31.01, 30.21, 39.22 ns (record notes).
chang_1978/kq_self#
{
"id": "kq_self",
"material": "Ar",
"file": "Ar/chang_1978__kq_self.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "primary",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "total",
"method": "laser-induced fluorescence after one-photon excitation from Ar(1s5) in a flowing afterglow, slope of the single-exponential decay rate against argon pressure (0.5-8 Torr)"
},
"uncertainty": {
"column": true,
"level": "not stated"
}
}
Table III (p. 3889), k_Q, the total two-body deactivation of 2p2, 2p3, 2p4, 2p7, 2p8, 2p9, 2p10 by ground-state argon, 2.0-11.0 x 10^-11 cm3/s, with the printed +- (’+-(10-20)%’, least squares, level not stated). 2p8 includes the transfer to 2p9 (k89 = 1.7): sadeghi_2001’s 2p8 value (0.24 x 10^-10) excludes it.
chang_1978/kq_self_bound#
{
"id": "kq_self_bound",
"material": "Ar",
"file": "Ar/chang_1978__kq_self_bound.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "check",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "total",
"method": "laser-induced fluorescence after one-photon excitation from Ar(1s5) in a flowing afterglow, slope of the decay rate against argon pressure (0.5-8 Torr)"
},
"uncertainty": {
"column": true,
"level": "bound"
}
}
Table III (p. 3889), 2p6: k_Q printed ‘<=1.8’, footnote b, ‘An upper limit determined from the slope of a plot such as shown in Fig. 4. The sum of k_nn’ is nearly equivalent to k_Q’ (0.8 + 0.8 + 0.2). Held as the interval 0 to 1.8 x 10^-11 cm3/s: value 0.9, bound half-width 0.9 (printed keeps ‘<=1.8’). sadeghi_2001’s 1.3 and nguyen_1978’s sum of transfers, 1.11, are inside it.
chang_1978/k_2p4#
{
"id": "k_2p4",
"material": "Ar",
"file": "Ar/chang_1978__k_2p4.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "primary",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "2p4",
"method": "laser-induced fluorescence after one-photon excitation from Ar(1s5) in a flowing afterglow, product-level time profile fitted with the rate equation (5)-(6)"
}
}
Table III (p. 3889), k_nn’ into 2p4 by argon: from 2p3, k34 = 2.2 x 10^-11 cm3/s. Rows are the initial levels. Assigned by fitting Eq. (6) to the product’s time profile (Fig. 6); no uncertainty stated. nguyen_1978: 2.75.
chang_1978/k_2p6#
{
"id": "k_2p6",
"material": "Ar",
"file": "Ar/chang_1978__k_2p6.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "primary",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "2p6",
"method": "laser-induced fluorescence after one-photon excitation from Ar(1s5) in a flowing afterglow, product-level time profile fitted with the rate equation (5)-(6)"
}
}
Table III (p. 3889), k_nn’ into 2p6 by argon: from 2p3, k36 = 4.1 x 10^-11 cm3/s. Rows are the initial levels. Assigned by fitting Eq. (6) to the product’s time profile (Fig. 6); no uncertainty stated. nguyen_1978: 4.4.
chang_1978/k_2p7#
{
"id": "k_2p7",
"material": "Ar",
"file": "Ar/chang_1978__k_2p7.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "primary",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "2p7",
"method": "laser-induced fluorescence after one-photon excitation from Ar(1s5) in a flowing afterglow, product-level time profile fitted with the rate equation (5)-(6)"
}
}
Table III (p. 3889), k_nn’ into 2p7 by argon: from 2p6, k67 = 0.8 x 10^-11 cm3/s. Rows are the initial levels. No uncertainty stated (the text: rate constants below 1e-11 are ‘difficult to determine’). nguyen_1978: 0.41.
chang_1978/k_2p8#
{
"id": "k_2p8",
"material": "Ar",
"file": "Ar/chang_1978__k_2p8.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "primary",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "2p8",
"method": "laser-induced fluorescence after one-photon excitation from Ar(1s5) in a flowing afterglow, product-level time profile fitted with the rate equation (5)-(6)"
}
}
Table III (p. 3889), k_nn’ into 2p8 by argon: from 2p6, k68 = 0.8, and from 2p7, k78 = 1.6 x 10^-11 cm3/s. Rows are the initial levels. No uncertainty stated. nguyen_1978: 0.6 and 1.43.
chang_1978/k_2p9#
{
"id": "k_2p9",
"material": "Ar",
"file": "Ar/chang_1978__k_2p9.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "primary",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "2p9",
"method": "laser-induced fluorescence after one-photon excitation from Ar(1s5) in a flowing afterglow, product-level time profile fitted with the rate equation (5)-(6)"
}
}
Table III (p. 3889), k_nn’ into 2p9 by argon: from 2p6, k69 = 0.2, and from 2p8, k89 = 1.7 x 10^-11 cm3/s. Rows are the initial levels. No uncertainty stated. nguyen_1978: 0.1 and 1.82; sadeghi_2001 quotes k89 as 0.18 x 10^-10 (refs. 9, 10).
chang_1978/k_2p3_db#
{
"id": "k_2p3_db",
"material": "Ar",
"file": "Ar/chang_1978__k_2p3_db.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "check",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "2p3",
"method": "detailed balance from the measured k34 (no temperature stated; 300 K reproduces it)"
}
}
Table III (p. 3889), 2p4 -> 2p3, k43 = 1.7 x 10^-11 cm3/s, footnote c: ‘Assigned using detailed balance and k34’ (2.2), not measured (script: 1.72 at 300 K from NIST’s energies). nguyen_1978 measured 2.3.
chang_1978/k_2p8_db#
{
"id": "k_2p8_db",
"material": "Ar",
"file": "Ar/chang_1978__k_2p8_db.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "check",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "2p8",
"method": "detailed balance from the measured k89 (no temperature stated; 300 K reproduces it)"
}
}
Table III (p. 3889), 2p9 -> 2p8, k98 = 0.6 x 10^-11 cm3/s, footnote c: ‘Assigned using detailed balance and k89’ (1.7), not measured (script: 0.58 at 300 K from NIST’s energies). nguyen_1978 measured 0.68.
chang_1978/k_4s#
{
"id": "k_4s",
"material": "Ar",
"file": "Ar/chang_1978__k_4s.csv",
"table": "tbl_dda0b9a86083",
"quantity": "collisional_quenching_rate_coefficient",
"unit": "cm3/s",
"scale": 1e-11,
"abscissa": "label",
"use": "check",
"parameters": {
"perturber": "self",
"order": 2,
"channel": "4s and 4s' manifold (sum)",
"method": "difference of the measured total k_Q and the measured state-to-state k_nn' to 4p, 4p' levels"
}
}
Table III (p. 3889), sum_m’ k_nm’, the intermultiplet transfer to the 4s and 4s’ manifold (‘not individually specified’), by difference k_Q - sum k_nn’ (the 4s products emit in the VUV and were not observed): 2p2 5.3, 2p3 4.7, 2p4 3.9, 2p7 6.1 (footnote e: 5.5 if k76 is allowed for), 2p10 2.0 x 10^-11 cm3/s. Derived, hence check. Not taken: 2p6 0.0 (its k_Q is an upper limit), 2p8 ‘<3.0’ and 2p9 ‘<3.5’.
chang_1978/A_4p_4s#
{
"id": "A_4p_4s",
"material": "Ar",
"file": "Ar/chang_1978__A_4p_4s.csv",
"table": "tbl_ea55ed0bd3cf",
"quantity": "transition_probability",
"unit": "1/s",
"scale": 1000000.0,
"abscissa": "label",
"use": "primary",
"parameters": {
"notation": "paschen"
},
"uncertainty": {
"relative": 0.1,
"level": "not stated"
}
}
Table IV (p. 3892), column CS, A_ki (10^6 s-1) of the 26 4p-4s lines of 2p2, 2p3, 2p4, 2p6-2p10: hollow-cathode branching ratios divided by Table II’s lifetimes. Rows and x are ‘upper-lower’ in Paschen notation (the record’s notes give NIST’s levels; printed air wavelengths, Angstrom, in printed). ‘Typically +-10%’, mainly the lifetimes’ (p. 3892), level not stated. CS / NIST: 0.89-1.14 for A >= 7e6 s-1 (record notes).
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.