MoLecutar Pusics, 1988, Vou. 64, No. 3, 425-436 Infrared Fourier transform spectroscopy of XeH by M. DOUAY, S. A, ROGERSt and P. F. BERNATHt Department of Chemistry, University of Arizona, Tucson, Arizona 85721, USA (Received 22 January 1988; accepted 26 January 1988) ‘The infrared emission spectrum of the Rydberg molecule XeH was recorded with the Kitt Peak Fourier transform spectrometer. XeH was made in a hollow ‘cathode discharge of 2-2torr H, and (1 tore Xe, The 0-0 bands of the C211— 8°" and the D*E*-C*T1 transitions were observed near 3250cm"' and 442m”, respectively. A rotational analysis provides spectroscopic constants for these states 1. Introduction More than 20 years ago, Michels and Harris [1] predicted the existence of bound excited states for the HeH molecule. This work, and more recent ab initio calculations on HeH [2-6], NeH [2, 7, 8] and ArH [2, 9-11], show that the excited states consist of an ionic core (HeH”, NH, AtH*) and a Rydberg electron, In these "Rydberg molecules” [12], the Rydberg electron contributes very little to the bonding, so the excited potential energy curves of the molecules closely resemble those of the corresponding ions. However, the ground X ** potential curves of the rare gas hydrides have only very shallow van der Waals minima. The first observed clectronic transition of a rare gas hydride molecule was reported by Johns in 1970 [13] for ArH. More recently, the spectra of HeH and NeH were reported in 1985 by Ketterle, Figger and Walther [14] and the spectra of KrH and KrD have been recorded for the first time by Dabrowski et al. [15]. In 1986 Lipson analysed transitions of XeH and XeD near 15000cm ! [16] in a Penning excitation source (Cossart lamp [17). Additional observations on XeH and XeD have been made by Dabrowski, Herzberg and Lipson [18] Brooks, Hunt and Miller [19-20] have published an account of a novel source for the production of HeH. They observed HeH emission spectra from the interface between helium gas and solid hydrogen when irradiated by a 15 MeV proton beam. In addition to these bound-bound observations of rare gas hydrides, several groups have detected bound-free emission [21-22]. They observed ultraviolet emis- sion from bound excited states to the repulsive wall of the shallow van der Waals ground state (X25), ‘The dissociation of HeH was also monitored by the detection of the neutral He and H fragments in charge-exchanged ion beam experiments [23-24]. Selgren and Gellene [25] have obtained some evidence for the metastability of ground state (or perhaps some excited state) of NeD. + Present address: Department of Chemistry, University of Colorado, Boulder, Colorado 80308, U.S.A. 4 Allred P. Sloan Fellow; Camille and Henry Dreyfus Teacher-Scholar426 M, Douay et al In the course of our work 0 the vibration-rotation spectrum of XeH* [26], we discovered two new infrared electronic transitions of KeH. A *1*5* transition near 3250em~! and a7 *-"TT transition near 4420em-' were assigned to Rydberg transitions of XeH. 2. Experimental The experimental details are identical to those reported in the XeH* paper (26). The XeH spectra were generated in a wates-cooled nickel hollow cathode discharge lamp at a current of 200mA. A slow, continuous flow of 2-2torr hydrogen and 100 mtorr xenon was maintained through the lamp. The molecular emission was recorded with the Fourier transform specisometer associated with the McMaih Solar Telescope of the National Solar Observatory at Kitt Peak. The 1800cm~'-5000cm~' region of the spectrum Was recorded at -020em resolution using liquid nitrogen cooled InSb detectors and a wedged Ge filter. The lower wavenumber limit was determined by the red limit of the detector, while the upper limit was et by the Ge filter. ‘Twenty scans Were co-added in 14 hours of integration. The interferogram was Fourier transformed imio a spectrum by G. Ladd of the National Solar Observa- tory. 3. Results ‘The XeH spectrum shows at least three transitions in the infrared, two of which were analysed. The spectrum was measured using a data reduction program devel- coped at the National Solar Observatory called DECOMP. All lines were fitted by & non-linear least-squares procedure to Voigt lineshape functions Xe has nine stable isotopes: 'Xe (0-1 per cent), #?°Xe (0-1 per cent), '?*Xe (19 per cent), '7°Xe (26:4 per cent), “Xe (44 per cent). 8!Xe (21-2 per cent), '*Xe (269 per cent), !*Xe (10-4 per cent), and Xe (8-9 per cent). Unfortunately, the isotopic structure was usually only partly resolved and the lines were broadened by ‘the presence of the different isotopes. For some R branch lines with J > 20:5, the expected isotopic pattern begins to appear as shown in figure 1. However, not enough lines with a clear isotope effect were observed to warrant separate fits for each isotopomer. Consequently, our fits were performed with the strongest feature in the isotopic pattern, This feature isa blend of the lines of the !2XeH and !!XeH molecules. As a result, the line positions and constants obtained in our work will be close to those for '?XeH and '"XeH. The signal-to-noise ratio for the strong lines was about 20 : 1. ‘The relative line positions could be determined to a precision of about +:0-002em”'. The absolute calibration of £0-001cm™~! was accomplished by observation of the vibration-rotation lines of OF {27} present as an impurity 3.4. The C*1-B7E* transition ‘This transition eceuts at 3250em ', It shows strong Q,, 02, Ry, Ra, P, and P; branches, but the spacing of adjacent lines of the Q, and Qs branches is very unusual for a ITE transition. As seen in figure 2, the Q, branch forms twa heads, one at J = 3:5 and one at J = 13°5 due to the large 7 value in the lower *5* state table 4)LR, spectra of Yet 47 i205) ‘aas0 7958.08 > Figure 1. Panel A is the Ry, (20-5) line of the 0-0 band of the C21-8*E* transition of XeH. The isotopic structure is just starting to be resolved, Pane! B is a stick spectrum of the same transition with the masses of the various Xe isotopes indicated. In Panel B, the height ofeach line is proportional to the isotopic abundance, but the wavenum. ber scale is not real, The wavenumber scale was established by spacing the lines proportionally to their masses with the overall width of the pattern set by comparison with Panel A. a { | qd O, | Ubu | Figure 2. A portion of the 0-0 band of the C*T1-B*E" transition of XeH. 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[As predicted by Earls [28] for a ®11 state in an intermediate Hund’s case (4 = A/ 2B 13), the most intense branches are Q,, Q2, Ri, Ra, Pi. and P; and the satelite branches, Qa, Oar. Ry2» Ras, Pras and Py branches are weaker. As expected, we saw the six main branches, but only four of the satellite branches (table 1). The Py and P,, branches were too weak to be identified (table 1). 3.2. The D?E*-C"M transition ‘The second transition near 4420cm™! has the appearance of a normal 7£*—"11 transition (figure 3). The °M1 state was found to be the same 7I1 state that was involved in the first transition near 3250cm-t, The six main branches were observed, along with five of the six weaker satellite branches (table 2). Only the P3, branch was not identified. ‘The upper ?£* state was found to be the upper state of the 2£*—*3:* transition observed by Lipson [16]. In agreement with Lipson, we found this state to be perturbed at J = 7-5 for the f parity component (N = 8, F,). & slight shift of the ¢ parity line at J = 35 (N = 3, F,) for the upper 7E* state was also present, No extra lines involving the perturbing state were identified in the spectrum, so a deperturba- tion analysis was not attempted. Figure 4 is an energy level diagram of the known low-lying states of XeH. The D?E"-42E* near 15000cm~* was observed by Lipson, while our two infrared transitions, D?E*-C 11 and C7M-B#E* casade from the D*5* state, The names of these electronic states are somewhat tentative since additional low-lying states are possible ‘A simultaneous, weighted, non-linear least-squares fit of all of the lines of the combined D?E*-C *M1-B75-* transitions was carried out. The hamiltonian matrix for each state was derived with Hund’s case (a) basis functions and diagonalized to produce the energy levels. The effective hamiltonian matrix of Brown et al. [29] was Utilized, An explicit listing of the *T1 matrix elements is provided in Table II of a paper by Amiot ef al. [30]. It was necessary to derive one additional matrix element, 22 FOS(44 8+ 9 +05, 12 £025 295 Gr +44 +05), where the definitions of Amiot et al. (30] are retained.LR, spectra of XeH 433, XeH 3250eni +18000em" io este) Figure 4. The low-lying states of XeH, The 7* matrix elements are also provided in Amiot et als paper [30], but we disagree with their matrix elements for j. 7» and 7y. For the customary spin- rotation hamilton fig = 8-8 +N + Nt + NY) the correct matrix elements are provided in table 3. The spectroscopic paramctes resulting from our fit ofthe lines of tables 1 and 2 are provided in tables 4, 5 and 6, Blended lines and perturbed lines were included in the final fit, but with reduced weight. ‘Table 3._ Hamiltonian matrix elements for a75* state in a case (a) party basis set. Tet 7 +050 ~05) ja f-05 0415) Be U+05I-05 yp ¢ +05 -057U +05) J CFOS +15) f205U + 1570 +05) D e-[U+ 05-09]? ye +05 -05)9 + 054 J-tu roses ™ Frosue rsa + 057 Hoe (U+05U—05] 1 ¢ +05U- 05/40 +05) F (G+ 050 + 1 F055 + 1540 +05)434 M, Douay et al Table 4. Spectroscopic constants (in em™') for the B*E* state of KeH, Too 7324-0398(29)1, ls 6386970(54) Dy x 10% 1.997420) Hy 10 4422) v0 7-4840531) Yoo 10% —1-6622(39) Fhe * 10" 4:96(13) nx 10"! 64415) +t The numbers in parentheses are one standard deviation inthe lat digit Table 5. Spectroscopic constants (in em") forthe C*T1 state of XeHL Teo 10$76-9827(28)1 Ay 816971013) Ba 6492172158) Dy x 108 1801320) Hy «10° 9.6421) te 032492142) ng x 108 1.77188) ag «10 836130) 4% 01086024) Go * 108 = 158014) Gh = 10° 407119) Po 02693442) Pon % 108 202451) Dae = 10° 27418) pax 10 112120) +The numbers in parentheses are one standard deviation inthe last digit Table 6. Spectroscopic constants (in em”) for the D#E* state of XeHL Constants This work Lipson Too 14998 921 14998-92193 By 64076610) 64077448) Dy x tot 2:1477(58) 220829) Hg x10? —9-96(95) vo 0-08505(89) 0.086030) Tog = 108 1735845 Ima 10 2.96(18) t Fixed to Lipson’s value (18). 4 The numbers in parentheses are one standard deviation in the last digit 4. Discussion 1n our experiment, XeH was produced in an electrica! discharge, but the chem- istry of a xenon and hydrogen plasma is different from that of the other rare gases plus hydrogen plasmas, As discussed in the XeH* paper [26], an excess of Hy provides the most favourable conditions for XeH production. XeH was not observed When I-2torr of Xe and 0-02torr of H were used in our hollow cathode discharge. When an excess of hydrogen is present, Hj is the dominant ion in theLR, spectra of XeH 435 discharge and will transfer a proton to Xe to produce XeH*. The XeH* ion then captures an electron to form excited XeH. The Xe cools by cascade emission of radiation and eventually dissociates into Xe and H atoms. [AS expected, there is good agreement between the observed spectroscopic con- stants of XeH1 (tables 4-6) and the corresponding values for XeH* [26]. Unfor- tunately, only 0-0 bands were observed for XeH, so vibrational constants and equilibrium molecular constants could not be derived, For the B25" transition (figure 4), a spin-rotation constant, 7, of 7-44em~! (table 4) was observed. Such a large value (greater than B) allowed the constants yp iw and 7, to be determined, A large 7 value for a ** state suggests that a *T1 state is nearby, bu this state was not directly observed. A simple pure precession estimate (= 1,4 = 60em_') indicates that the missing B’TT state is about 200cm~t above the BPE" state. A few weak branches could be picked out near 3200em~', but analysis was not possible. In keeping with spectroscopic custom, we have labelled the low-lying XeH states as X25, 475°, B25", CAM and D2E*, Our work on the D2E* and CMI states is in agreement with, but more accurate than, the previous analyses [16, 18]. The discovery of the BE state and the indirect evidence for a B'IT state represents ‘our main contribution to the spectroscopy of KeH. We have resisted the temptation to assign atom n! quantum numbers to the Rydberg states of XeH. We suspect that nand | are probably poor quantum numbers for the 4, B, C and D states of XeH and some ab initio theoretical guidance would be very helpful ‘The National Solar Observatory is operated by the Association for Research in Astronomy, Inc, under contract with the National Science Foundation, We thank J. Wagner for technical assistance in acquiring the spectra. This research was sup- ported by the Air Fores Astronauties Laboratory (F 04611-87-K-0020), References. [1] Mics, H. HL, and Hanus, F. 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