Abstract
We analyze the basic thermodynamic, kinetic, radiative, and spectroscopic properties of halogen and interhalogen molecules which are potentially suitable for the construction of visible and near-IR chemical lasers. We discuss the problem of chemical buildup of electronically excited states (EES) of donor molecules (or atoms). We propose a number of new kinetic schemes with formation of EES of donor particles, for the development of lasers based on electronic transitions (ET). We obtain analytic relations for the lasing condition and for the laser efficiency of a system of a “donor—acceptor” type as applied to ET chemical lasers. Actual results of research into the gain properties and energy characteristics of potential visible-band chemical NF-IF and N2-IF lasers. The possibility of using atoms in chemical lasers is discussed.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Handbook of Chemical Lasers, R. W. F. Gross and J. F. Bott, (eds.), Wiley (1976).
A. S. Kakshin, V. I. Igoshin, A. N. Oraevskii, and V. A. Shcheglov, Chemical Lasers [in Russian], Nauka, Moscow (1982).
A. A. Stepanov and V. A. Shcheglov, “CW chemical lasers using reaction products (survey),” Kvant. Élektron.,9, No. 6, 1077–1126 (1982).
A. A. Stepanov, V. A. Shcheglov, and N. N. Yuryshev, “Exchange-type cw chemical lasers (survey),” Kvant. Élektron.,12, No. 6, 1127–1173 (1985).
A. T. Pritt, R. D. Coombe, D. Pilipovich, R. I. Wagner, D. Benard, and C. Dymek, “Chemical generation of a population inversion between the spin-orbit states of atomic iodine,” Appl. Phys. Lett.,31, 745–747 (1977).
W. F. McDermott, N. R. Pchelkin, D. J. Benard, and R. R. Bousek, “An electronic transition chemical laser,” ibid., 32, 469–470 (1978).
V. F. Gavrikov, N. A. Konoplev, I. V. Mel’nikov, and V. A. Shcheglov, “Chemical laser on electron transitions of IF molecules,” Kvant. Élektron., 13, 544–550 (1986).
N. G. Basov, V. F. Gavrikov, and V. A. Shcheglov, “Exchange chemical visible-light and IR lasers on electron transitions of halogens and interhalogens,” ibid.,14, 1754–1771 (1987).
N. G. Basov, V. F. Gavrikov, S. A. Pozdneev, and V. A. Shcheglov, “Feasibility of expanding the spectral range of the emission of chemical lasers based on electron transitions,” ibid.,14, 1787–1806 (1987).
N. G. Basov, V. F. Gavrikov, and V. A. Shcheglov, “Chemical lasers for the visible and near IR bands,” Izv. Akad. Nauk SSSR, Ser. Fiz.,51, No. 8, 1404–1418 (1987).
R. L. Byer, R. L. Herbst, H. Kidal, and M.D. Levenson, “Optically pumped molecular iodine vapor-phase laser,” Appl. Phys. Lett.,20, No. 11, 463–468 (1972).
S. J. Davis and L. Hanko, “Optically pumped iodine-monofluoride B3η (0+) → X1Σ+ laser,” ibid.,37, No. 12, 692–694 (1980).
S. J. Davis, L. Hanko, and R. F. Shea, “Iodine monofluoride B3η(0+) → X1Σ+ from collisionally pumped states,” J. Chem. Phys.,78, No. 1, 172–182 (1983).
S. J. Davis, L. Hanko, and P. J. Wolf, “Continuous wave optically pumped iodine monofluoride B3η(0+ → X1Σ+ laser,” ibid.,82, No. 11, 4831–4837 (1985).
M. C. Heaven, “Fluorescence decay dynamics of the halogens and interhalogens,” Chem. Soc. Rev.,15, No. 4, 405–548 (1986).
W. J. Marinelly and L. G. Piper, “Franck-Condon factors and absolute transition probabilities for the IF (B3η0+ → X1Σ+ transition,” J. Quant. Spectrosc. Radiat. Transfer,34, No. 4, 321–330 (1985).
W. G. Brown and G. E. Gibson, “Predissociation of the spectrum of iodine chloride,” Phys. Rev.,40, No. 2, 529–443 (1932).
M. A. A. Clyne and I. S. McDermid, “Quantum-resolved dynamics of excited states. Pt. 4: Radiative and predissociative lifetimes of IF (B3η (0+)),” J. Chem. Soc. Faraday Trans. II,74, No. 8, 1644–1661 (1978).
K.-P. Huber and H. Hertzberg, Constants of Diatomic Molecules, Van Nostrand (1979).
J.-P. Nicolai and M. C. Heaven, “Laser excitation spectra for matrix isolated IF. Observation of new low-lying electronic states,” J. Chem. Phys.,87, No. 6, 3304–3312 (1987).
P. J. Wolf and S. J. Davis, “Collisional dynamics of the IF (B3η (0+) state. II. Electronic quenching at low pressures,” ibid.,83, No. 1, 91–99 (1985).
J. J. Steinfeld, “Rate data for inelastic collision process in the diatomic halogen molecule,“ J. Chem. Phys. Ref. Data13, No. 2, 445–553 (1984).
P. J. Wolf, J. H. Glover, L. Hanko, R. F. Shea, S. J. Davis, “Collisional dynamics of the IF (B3η (0+)) state. I: Pulsed excitation studies of v=3 and 4 at high pressure,” J. Chem. Phys., 82, No. 5, 2321–2329 (1985).
M. A. A. Clyne and L. C. Zai, “Studies of BrCl by laser-induced fluorescence. 4. Lower levels (v’ ≤ 3) of the B3η (0+) manifold,” J. Chem. Soc. Faraday Trans. II.,78, No. 8, 1221–1229 (1982).
M. A. A. Clyne and J. P. Liddy, “Quantum-resolved dynamics of excited states. 6: Radiative lifetime and collisional deactivation rates in BrF(B),” ibid.,76, No. 12, 1569–1685 (1980).
P. J. Wolf and S. J. Davis, “Collisional dynamics of the IF(B3η (0+)) state. III. Vibrational and rotational energy transfer,” J. Chem. Phys.,87, No. 6, 3492–3508 (1987).
Y. Qiu, Z. Zhou, and S. Liu, “Reactions of fluorine atoms with iodides studied by crossed beam laser-induced fluorescence,” Chem. Phys. Lett.,136, No. 2, 187–191 (1987).
M. A. A. Clyne and S. Toby, “Formation of excited BrCl (B3η (0+)) in the reaction of bromine with chlorine dioxide,” J. Photochem.,11, No. 1, 87–100 (1979).
R. A. Durie, “The electronic emission spectrum and molecular constants of iodine monofluoride,” Canad. J. Phys.,44, No. 2, 337–352 (1966).
J. W. Birks, S. D. Gabelnic, and H. S. Johnston, “Chemiluminescence of IF in the gas phase of I2 with F2,” J. Mol. Spectr.,57, No. 1, 23–46 (1975).
J. Valentini, M. J. Coggiola, and Y. T. Lee, “Molecular beam study of F2+I2 reactions,” Intern. J. Chem. Kinet.,8, No. 8, 605–608 (1976).
R. G. Coombe and P. K. Horn, “Chemiluminescent reactions of O2F. 2. Reactions producing excited BrF and IF,” J. Phys. Chem.,83, No. 19, 2435–2440 (1979).
R. V. Lilenfeld and G. R. Bradlurn, “Observation of atomic iodine formed during the room-temperature reaction between F2 and I2,” Chem. Phys. Lett.,131, No. 3, 276–278 (1986).
B. Girard, N. Billy, G. Gouedard, and J. Vigue, “LIF study of the I2+F → IF+I reaction population of the v=0 level of the IF,” ibid.,136, No. 1, 101–105 (1987).
H. S. Braynis, D. Raybone, and J. C. Whitehead, “Chemiluminescent reactions of fluorine atoms with organic iodides in the gas phase, Pt. 1.: Iodomethane; Pt. 2: Aliphatic and aromatic iodides,” J. Chem. Soc. Faraday Trans. II,83, 627–637 (1987).
D. Raybone, T. M. Watkinson, and J. C. Whitehead, “Chemiluminescent reactions of fluorine atoms with inorganic iodides in the gas phase,” ibid.,83, 767–773 (1987).
P. D. Whitefield, “A review of studies investigating a potential chemical laser pumping scheme: IF (B3η (0+)) pumping by energy transfer from O2 (1Δ) to IF (X1Σ+), J. Photochem.,25, No. 2/4, 465–473 (1984).
D. Raybone, T. M. Watkins, and J. C. Whitehead, “The production of longlived IF (B3η (0+)) emission in the 248 nm photolysis of a mixture of CF3I and F2, Chem. Phys. Lett.,139, No. 5, 442–447 (1987).
D. K. Neumann, S. R. Czyzak, C. H. Muller III, and D. J. Stech,“ IF (B3η (0+)) chemiluminescence resulting from laser photolysis of mixture of O2 and O3F7I,” ibid.,131, No. 1/2, 1420–1423 (1986).
M. A. A. Clyne, J. A. Coxoh, and L. W. Townsend, “Formation of B3η (0+) states of BrF and IF by atom recombination in the presence of singlet (1Δg,1Σ +g ) oxygen,” J. Chem. Soc. Faraday Trans. III.,68, No. 12, 2134–2143 (1972).
P. D. Whitfield, S. F. Davis, and R. F. Shea, “Singlet molecular oxygen pumping of B3η (0+),ȁ J. Chem. Phys.,78, No. 11, 6793–6801 (1983).
G. W. Tregay, J. W. Raymonda, and H. M. Thompson, “Production of electronically excited iodine monofluoride by energy transfer from vibrationally excited hydrogen fluoride,ȁ Chem. Phys. Lett.,123, No. 5, 458–462 (1986).
L. G. Piper, W. J. Marinelly, W. T. Rawlins, and B. D. Green, “The excitation of IF (B3η (0+)) by N2(A3Σ +u ),ȁ J. Chem. Phys.,83, No. 11, 5602–5609 (1985).
D. Lin and D. W. Setser, “Flowing-afterglow source of NF (b1σ+): Measurement of quenching rate constants,ȁ J. Phys. Chem.,89, No. 9, 1561–1564 (1985).
K. A. Mohamed, B. N. Khanna, and K. M. Lal, “Franck-Condon factors and r-centroids for the b1Σ+ — X3Σ− band system of NF,” Indian J. Pure Appl. Phys.,12, No. 3, 243–244 (1974).
J.W. McGowan, R. H. Kummler, and F. R. Gilmore, The Excited State in Chemical Physics, Plenum, N. Y. (1975), pp. 379–430.
A. A. Radtsig and B. M. Smirnov, Handbook of Atomic and Molecular Physics [in Russian], Atomizdat, Moscow (1980).
A. N. Oraevskii, “Onset of negative temperatures in chemical reactions,” Zh. Éksp. Teor. Fiz.,45, No. 2, 177–179 (1963).
A. S. Bashkin and A. N. Oraevskii, “Photorecombination lasers (survey),” Kvant. Élektron., No. 1, 5–29 (1973).
A. S. Bashkin and A. N. Oraevskii, “On the problem of production of cw recombination lasers,” ibid.,3, No. 1, 29–34 (1976).
V. A. Kochelap and Yu. A. Kukibnyi, “Gasdynamic photorecombination lasers,” ibid.,2, No. 7, 1471–1480 (1975).
I. A. Izmailov, V. A. Kochelap, and Yu. A. Kukibnyi, “Coefficient of light amplification in photorecombination processes,” Ukr. Fiz. Zh.,21, No. 3, 508–510 (1976).
A. S. Bashkin, V. I. Igoshin, A. I. Nikitin, and A. N. Oraevskii, Chemical Lasers [in Russian], VINITI, Moscow (1975).
A. I. Lidyukov, Yu. A. Kulagin, S. A. Reshetnyak, and L. A. Shelepin, Metastable Electronic States and Kinetics of Active Media, FIAN Preprint No. 239, Moscow (1982).
N. G. Basov, V. F. Gavrikov, S. A. Pozdneev, and V. A. Shcheglov, Chemical Lasers on Electronic Transitions. II. New Lasers with Chain Excitation, FIAN Preprint No. 304, Moscow (1986).
N. G. Basov, V. F. Gavrikov, S. A. Pozdneev, and V. A. Shcheglov, “New type of chemical lasers with electronic transitions and chain mechanism of excitation,” Kvant. Élektron.,14, No. 9, 1772–1786 (1987).
T. D. Trelling and D. W. Setser, “Quenching of N2 (A3Σ +u ) by Hg (II) halides,” Chem. Phys. Lett.,74, No. 2, 211–217 (1980).
W. W. Rice and R. J. Jensen, “Aluminum fluoride exploding-wire laser,” Appl. Phys. Lett.,22, No. 1, 67–68 (1973).
J. D. Koker and W. W. Rice, “Magnesium fluoride metal atom oxidation laser from explosively generated metal vapor,” J. Appl. Phys.,45, No. 6, 2770–2772 (1974).
W. W. Rice and W. H. Beattle, “Metal atom oxidation lasers,” Chem. Phys. Lett.,19, No. 1, 82–85 (1973).
W. W. Rice, “Metal atom oxidation lasers: A new family of chemical lasers,” IEEE J. Quant. Electron.,QE-11, No. 8, 689–690 (1975).
C. R. Jones and H. P. Broida, “An efficient chemiluminescent reaction,” J. Chem. Phys.,59, No. 12, 6677–6678 (1973).
D. J. Eckstrom, S. A. Edelstain, and S. W. Benson, “Chemiluminescence photon yields for several alkaline earth metal-halogen/oxygen reactions,” ibid.,60, No. 7, 2930–2931 (1974).
D. J. Eckstrom, S. A. Edelstain, D. L. Huestis, M. Luria, B. E. Perry, and S. W. Benson, “Studies of visible chemical lasers based on reactions of metal atoms with various exidizers,” IEEE J. Quant. Electron.,QE-11, No. 8, 691 (1975).
L. E. Wilson, S. G. Hadly, R. A. Harris, and G. Hager, “The potential for electronic transition laser with molecules from carbon group oxides,” ibid.,QE-11, No. 8, 691 (1975).
G. L. Schott, S. W. Rabidean, A. V. Nowak, and R. W. Getzinger, “Can we beat F2 and H2 for HF lasers?” ibid.,QE-11, No. 8, 690 (1975).
F. Engelke and R. N. Zare, “Crossed-beam chemiluminescence: The alkaline earth rearrangement reaction M+S2Cl2 → S2+MCl2,” Chem. Phys.,19, No. 3, 327–340 (1977).
A. S. Bashkin, N. L. Kupriyanov, and A. N. Oraevskii, “Feasibility of a chemically pumped S2-molecule visible-band laser,” Kvant. Élektron.,5, No. 2, 421–423 (1978).
D. O. Ham, “Energy limits in chemiluminescent atom transfer reactions: Bond dissociation energy of NaF,” J. Chem. Phys.,60, No. 5, 1802–1805 (1974).
W. S. Struve, J. R. Krenos, S. P. McFadden, and D. R. Herchbach, “Molecular beam kinetics: Angular distributions and chemiluminescence reactions of alkali dimers with halogen atoms and molecules,” ibid.,62, No. 2, 404–419 (1975).
J. R. Krenos and J. C. Tully, “Statistical partitioning of electronic energy: Reactions of alkali dimers with halogen atoms,” ibid.,62, No. 2, 420–424 (1975).
Excimer Lasers, C. M. Rhoades, (ed.), [Russian translation], Mir, Moscow (1981).
V. S. Zuev, S. B. Kormer, L. D. Mikheev, M. V. Sinitsyn, I. I. Sobel’man, and G. I. Startsev, “Onset of inversion on a molecular sulfur transition in COS photodissociation,” Pis’ma v ZhÉTF,16, No. 4, 222–224 (1972).
H. F. Krause, S. G. Johnson, S. Datz, and F. K. Schmidt-Bleek, “Crossed molecular beam study of excited atom reactions of Hg(63P 02 ) with Cl2 and chlorinated methane molecules,” Chem. Phys. Lett.,31, No. 3, 577–578 (1975).
M. W. McGeogh, G. R. Furnier, and P. Ewart, “Visible continue of the cadmium mercury molecule,” J. Phys. B,9, No. 5, L121-L125 (1976).
J. J. Wright and L. S. Balling, VAlkali-SCl2 chemiluminescence. Vibrational population inversion in the B state of S2,” Chem. Phys. Let.,108, No. 3, 214–221 (1984).
H. B. Palmer and W. J. Miller, “Energy distribution in products of the reaction of C atoms with CH and CCl,” J. Chem. Phys.,38, No. 1, 278–279 (1963).
H. B. Palmer and W. J. Miller, “Chemiluminescence and radical reactions in diffusion flame of alkali metals with organic halides,” ibid.,40, No. 2, 3701–3715 (1964).
P. W. Naegeli and H. B. Palmer, “Creation of population inversion in the A3IIg state of C2 by chemical reaction,” ibid.,48, No. 4, 2372–2373 (1968).
M. Polanyi, Atomic Reactions, Williams and Norgate, London (1932).
N. G. Basov, V. F. Gavrikov, L. I. Lvov, I. V. Melnikov, and V. A. Shcheglov, “Chemical lasers on electronic transitions. 1. Transfer lasers on halogens, interhalogens, and other molecules,” Preprint No. 348, Lebedev Phys. Inst., Moscow (1985).
J. M. Herbelin and N. Cohen, “The chemical production of electronically excited state in the H/NF2 system,” Chem. Phys. Lett.,20, No. 6, 605–609 (1973).
A. T. Pritt and R. D. Coombe, “Azide mechanisms for production of NCl metastables,” J. Chem. Kinet.,12, No. 10, 741–753 (1980).
A. T. Pritt and R. D. Coombe, “Production of electronically excited NF by the reaction of fluorine atoms with NH3,” Chem. Phys. Lett.,58, No. 4, 606 (1978).
W. Hack and O. Horie, “Production of electronically excited NF radicals in the system NH3—F—O2(1Δg),” ibid.,82, No. 2, 327–330 (1981).
J. M. Herbelin, D. J. Spencer, and M. A. Kwok, “Scale-up NF (a 1Δ) produced by the H+NF2 system in subsonic CW laser device,” J. Appl. Phys.,48, No. 7, 3050–3052 (1977).
A. T. Pritt, D. Patel, and B. J. Benard, “Iodine monofluoride resonant energy transfer chemiluminescence,” Chem. Phys. Lett.,97, No. 4/5, 471–475 (1983).
J. M. Heberlin, M. A. Kwok, and D. J. Spencer, “Enhancement of NF (b1Σ+) by iodine laser pumping,” J. Appl. Phys.,49, No. 7, 3750–3752 (1978).
N. V. Shinkarenko and V. B. Aleskovskii, “Singlet oxygen, method of obtaining and observing,” Usp. Khim.,50, No. 3, 406–428 (1981).
H. H. Wasserman and J. R. Scheffer, “Singlet oxygen reactions from photoperoxides,” J. Amer. Chem. Soc.,89, No. 12, 3073–3075 (1967).
E. Wasserman, R. W. Murray, M. L. Kaplan, and W. A. Yager, “Electron paramagnetic resonance of1Δ oxygen from a phosphite-ozone complex,” J. Am. Chem. Soc.,90, No. 15, 4160–4164 (1968).
D. R. Kearns, “Physical and chemical properties of singlet molecular oxygen,” Chem. Rev.,71, No. 4, 395–427 (1971).
S. R. Abbott, S. Ness, and D. M. Hercules, “Chemiluminescence from peroxide decomposition reactions. The role of energy transfer,” J. Am. Chem. Soc.,92, No. 5, 1128–1136 (1970).
T. C. Clark and M. A. A. Clyne, “Kinetics of chemiluminescent reactions of the gaseous azide radical,” J. Chem. Soc. Faraday Trans. II,66, No. 4, 877–885 (1970).
J. G. Piper, R. H. Krech, and R. L. Taylor, Generation of N2 in the thermal decomposition of NaN3,” J. Chem. Phys.,74, No. 5, 2099–2104 (1979).
K. Yamasaki, T. Fueno, and O. Kafimoto, “Studies on the reaction N+N3 → N2(B3IIg)+N2 (X1Σ +g ),” Chem. Phys. Lett.,94, No. 4, 425–429 (1983).
D. S. Bystrov, A. F. Vilesov, A. M. Pravilov, and L. G. Smirnova, “Luminescence kinetics in the first positive and Y systems of N2 upon recombination of N(4S) atoms,” Khim. Fizika,6, No. 9, 1173–1182 (1987).
A. F. Vilesov, A. M. Pravilov, and L. G. Smirnova, “Mechanism of chemiluminescence in recombination of N(4S) atoms,” Khim. Fizika,6, No. 9, 1183–1191 (1987).
A. N. Dvoryankin, Yu. A. Kulagin, and L. A. Shelepin, “Kinetics of relaxation of electron-excited states of nitrogen molecules in a gas stream,” School—Conference on Fundamental Problems of Shock-Wave Physics, Azau (1987). Chernogolovka Abstracts, (1987), pp. 296–297.
R. Pearson, Symmetry Rules in Chemical Reactions [Russian translation], Mir (1979).
E. E. Nikitin and S. Ya. Umanskii, Nonadiabatic Transitions in Slow Atomic Collisions [in Russian], Atomizdat, Moscow (1979).
V. M. Galitskii, E. E. Nikitin, and B. M. Smirnov, Theory of Collisions of Atomic Particles [in Russian], Nauka, (1981).
A. N. Dvoryankin, L. B. Ibragimova, Yu. A. Kulagin, and L. A. Shelepin, “Electron relaxation mechanisms in atomic-molecular media,” in: Plazma Chemistry, B. M. Smirnov, (ed.), Énergoatomizdat, Moscow, No. 14 (1987), pp. 102–127.
I. A. Izmailov, V. A. Kochelap, and L. Yu. Mel’nikov, “Population inversion of diatomic molecules in transfer of electron excitation from metastable nitrogen,” Atom. Énerg., No. 32, 3–13 (1987).
H. Cha and D.W. Setser, “NF(b1Σ) quenching rate constants by halogens and interhalogens and the excitation rate constant for IF (B) formation,” J. Phys. Chem.,91, No. 12, 3758–3767 (1978).
D. J. Benard, M. A. Chowdhury, and A. T. Pritt, “Quenching of NF singlet states in a hybrid chemical laser system,” J. Appl. Phys.,60, No. 12, 4051–4058 (1986).
S. J. David and R. D. Coombe, “The chemiluminescence reactions of N(4S) atoms with azide radicals,” J. Phys. Chem.,89, No. 24, 5206–5219 (1985).
L. G. Piper, W. J. Marinelly, W. T. Rawlins, and B. D. Green, “The excitation of IF (B3II0+) by N2 (A3Σ +u ),” J. Chem. Phys.,83, No. 11, 5602–5609 (1985).
S. J. David, A. P. Ongstad, M. A. McDonald, and R. D. Coombe, “Chemical generation of excited IF (B3II0+),” Chem. Phys. Lett.,136, Nos. 3/4, 352–357 (1987).
W. G. Klark and D. W. Setser, “Energy transfer reactions of N2. 5: Quenching by hydrogen halides, metal halides, and other molecules,” J. Phys. Chem.,84, No. 18, 2223–2225 (1980).
J. Deparasinka, J. A. Beswick, and A. Tramer, “Distorted wave calculation for electronic energy transfer in molecular collisions,” J. Chem. Phys.,71, No. 6, 2477–2487 (1979).
A. Mandl and J. J. Ewing, “Quenching of N2 (A3∑ +u ) by I2,” ibid.,67, No. 8, 3490–3494 (1977).
T. D. Drelling and D. W. Setser, “Quenching of N2 (A3∑ +u ) by Hg(II) halides,” Chem. Phys. Lett.,74, No. 2, 211–217 (1980).
N. G. Basov, V. F. Gavrikov, A. N. Dvoryankin, and V. A. Shcheglov, “Chemical generator of electron-excited nitrogen N2 (A, B). Feasibility of a visible-band (λ=625 nm) N2(A)-IF laser,” FIAN Preprint No. 136, Moscow (1988).
Additional information
Translated from Trudy Fizicheskogo Instituta im. P. N. Lebedeva Akademiya Nauk SSSR, Vol. 194, pp. 171–211, 1989.
Rights and permissions
About this article
Cite this article
Gavrikov, V.F., Dvoryankin, A.N., Stepanov, A.A. et al. Visible and near-infrared chemical lasers. J Russ Laser Res 15, 177–212 (1994). https://doi.org/10.1007/BF02581029
Issue Date:
DOI: https://doi.org/10.1007/BF02581029