1932

Abstract

This review focuses on experimental studies of the dynamical outcomes following collisional quenching of electronically excited OH 2Σ+ radicals by molecular partners. The experimental observables include the branching between reactive and nonreactive decay channels, kinetic energy release, and quantum state distributions of the products. Complementary theoretical investigations reveal regions of strong nonadiabatic coupling, known as conical intersections, which facilitate the quenching process. The dynamical outcomes observed experimentally are connected to the local forces and geometric properties of the nuclei in the conical intersection region. Dynamical calculations for the benchmark OH-H system are in good accord with experimental observations, demonstrating that the outcomes reflect the strong coupling in the conical intersection region as the system evolves from the excited electronic state to quenched products.

Associated Article

There are media items related to this article:
Dynamical Outcomes of Quenching: Reflections on a Conical Intersection: Video 2

Associated Article

There are media items related to this article:
Dynamical Outcomes of Quenching: Reflections on a Conical Intersection: Video 1

Associated Article

There are media items related to this article:
Dynamical Outcomes of Quenching: Reflections on a Conical Intersection: Video 3
Loading

Article metrics loading...

/content/journals/10.1146/annurev-physchem-040513-103628
2014-04-01
2024-03-29
Loading full text...

Full text loading...

/deliver/fulltext/physchem/65/1/annurev-physchem-040513-103628.html?itemId=/content/journals/10.1146/annurev-physchem-040513-103628&mimeType=html&fmt=ahah

Literature Cited

  1. Glassman I, Yetter R. 1.  2008. Combustion Boston: Academic, 4th ed..
  2. Wayne RP. 2.  2000. Chemistry of Atmospheres New York: Oxford Univ. Press, 3rd ed..
  3. Luque J, Crosley DR. 3.  1999. LIFBASE: Database and Spectral Simulation Program (Version 1.6) SRI Int. Rep. MP 99-009, SRI Int., Menlo Park, CA [Google Scholar]
  4. Copeland RA, Crosley DR. 4.  1986. Temperature dependent electronic quenching of OH(A2Σ+, v′ = 0) between 230 and 310 K. J. Chem. Phys. 84:3099–105 [Google Scholar]
  5. Heard DE, Henderson DA. 5.  2000. Quenching of OH(A2Σ+, v′ = 0) by several collision partners between 200 and 344 K: cross-section measurements and model comparisons. Phys. Chem. Chem. Phys. 2:67–72 [Google Scholar]
  6. Retail B, Orr-Ewing AJ. 6.  2010. Processes involving multiple potential energy surfaces. Tutorials in Molecular Reaction Dynamics M Brouard, C Vallance 88–115 Cambridge, UK: R. Soc. Chem. [Google Scholar]
  7. Crim FF. 7.  2012. Molecular reaction dynamics across the phases: similarities and differences. Faraday Discuss. 157:9–26 [Google Scholar]
  8. Domcke W, Yarkony DR. 8.  2012. Role of conical intersections in molecular spectroscopy and photoinduced chemical dynamics. Annu. Rev. Phys. Chem. 63:325–52 [Google Scholar]
  9. Levine BG, Martinez TJ. 9.  2007. Isomerization through conical intersections. Annu. Rev. Phys. Chem. 58:613–34 [Google Scholar]
  10. Matsika S, Krause P. 10.  2011. Nonadiabatic events and conical intersections. Annu. Rev. Phys. Chem. 62:621–43 [Google Scholar]
  11. Worth GA, Cederbaum LS. 11.  2004. Beyond Born-Oppenheimer: molecular dynamics through a conical intersection. Annu. Rev. Phys. Chem. 55:127–58 [Google Scholar]
  12. Pollack IB, Lei YX, Stephenson TA, Lester MI. 12.  2006. Electronic quenching of OH A2Σ+ radicals in collisions with molecular hydrogen. Chem. Phys. Lett. 421:324–28 [Google Scholar]
  13. Dempsey LP, Murray C, Lester MI. 13.  2007. Product branching between reactive and non-reactive pathways in the collisional quenching of OH A2Σ+ radicals by H2. J. Chem. Phys. 127:151101 [Google Scholar]
  14. Dempsey LP, Murray C, Cleary PA, Lester MI. 14.  2008. Electronic quenching of OH A2Σ+ radicals in single collision events with H2 and D2: a comprehensive quantum state distribution of the OH X2Π products. Phys. Chem. Chem. Phys. 10:1424–32 [Google Scholar]
  15. Dempsey LP, Sechler TD, Murray C, Lester MI. 15.  2009. Quantum state distribution of the OH X2Π products from collisional quenching of OH A2Σ+ by O2 and CO2. J. Phys. Chem. A 113:6851–58 [Google Scholar]
  16. Cleary PA, Dempsey LP, Murray C, Lester MI, Kłos J, Alexander MH. 16.  2007. Electronic quenching of OH A2Σ+ radicals in single collision events with molecular hydrogen: quantum state distribution of the OH X2Π products. J. Chem. Phys. 126:204316 [Google Scholar]
  17. Lehman JH, Dempsey LP, Lester MI, Fu B, Kamarchik E, Bowman JM. 17.  2010. Collisional quenching of OD A2Σ+ by H2: experimental and theoretical studies of the state-resolved OD X2Π product distribution and branching fraction. J. Chem. Phys. 133:164307 [Google Scholar]
  18. Dempsey LP, Sechler TD, Murray C, Lester MI, Matsika S. 18.  2009. State-resolved distribution of OH X2Π products arising from electronic quenching of OH A2Σ+ by N2. J. Chem. Phys. 130:104307 [Google Scholar]
  19. Lehman JH, Lester MI, Kłos J, Alexander MH, Dagdigian PJ. 19.  et al. 2013. Electronic quenching of OH A2Σ+ induced by collisions with Kr atoms. J. Phys. Chem. A 11713481–90
  20. Lehman JH, Lester MI, Yarkony DR. 20.  2012. Reactive quenching of OH A2Σ+ by O2 and CO: experimental and nonadiabatic theoretical studies of H- and O-atom product channels. J. Chem. Phys. 137:094312 [Google Scholar]
  21. Anderson DT, Todd MW, Lester MI. 21.  1999. Reactive quenching of electronically excited OH radicals in collisions with molecular hydrogen. J. Chem. Phys. 110:11117–20 [Google Scholar]
  22. Todd MW, Anderson DT, Lester MI. 22.  2001. Reactive quenching of OH A2Σ+ in collisions with molecular deuterium via nonadiabatic passage through a conical intersection. J. Phys. Chem. A 105:10031–36 [Google Scholar]
  23. Lehman JH, Bertrand JL, Stephenson TA, Lester MI. 23.  2011. Reactive quenching of OD A2Σ+ by H2: translational energy distributions for H- and D-atom product channels. J. Chem. Phys. 135:144303 [Google Scholar]
  24. Ortiz-Suárez M, Witinski MF, Davis HF. 24.  2006. Reactive quenching of OH(A2Σ+) by D2 studied using crossed molecular beams. J. Chem. Phys. 124:201106 [Google Scholar]
  25. Lester MI, Loomis RA, Schwartz RL, Walch SP. 25.  1997. Electronic quenching of OH A2Σ+ (v′ = 0, 1) in complexes with hydrogen and nitrogen. J. Phys. Chem. A 101:9195–206 [Google Scholar]
  26. Hoffman BC, Yarkony DR. 26.  2000. The role of conical intersections in the nonadiabatic quenching of OH(A2Σ+) by molecular hydrogen. J. Chem. Phys. 113:10091–99 [Google Scholar]
  27. Kamarchik E, Fu BN, Bowman JM. 27.  2010. Communication: classical trajectory study of the postquenching dynamics of OH A2Σ+ by H2 initiated at conical intersections. J. Chem. Phys. 132:091102 [Google Scholar]
  28. Fu B, Kamarchik E, Bowman JM. 28.  2010. Quasiclassical trajectory study of the postquenching dynamics of OH A2Σ+ by H2/D2 on a global potential energy surface. J. Chem. Phys. 133:164306 [Google Scholar]
  29. Zhang PY, Lu RF, Chu TS, Han KL. 29.  2010. Quenching of OH(A2Σ+) by H2 through conical intersections: highly excited products in nonreactive channel. J. Phys. Chem. A 114:6565–68 [Google Scholar]
  30. Zhang PY, Lu RF, Chu TS, Han KL. 30.  2010. Nonadiabatic quantum reactive scattering of the OH(A2Σ+) + D2. J. Chem. Phys. 133:174316 [Google Scholar]
  31. Collins MA, Godsi O, Liu S, Zhang DH. 31.  2011. An ab initio quasi-diabatic potential energy matrix for OH(2Σ+) + H2. J. Chem. Phys. 135:234307 [Google Scholar]
  32. Copeland RA, Dyer MJ, Crosley DR. 32.  1985. Rotational-level-dependent quenching of A2Σ+ OH and OD. J. Chem. Phys. 82:4022–32 [Google Scholar]
  33. Fairchild PW, Smith GP, Crosley DR. 33.  1983. Collisional quenching of A2Σ+ hydroxyl at elevated temperatures. J. Chem. Phys. 79:1795–807 [Google Scholar]
  34. Kenner RD, Capetanakis FP, Stuhl F. 34.  1990. Kinetic isotope effects in the electronic quenching of OD/OH(A2Σ+, v = 0) at 296 ± 4 K. J. Phys. Chem. 94:2441–46 [Google Scholar]
  35. Smith GP, Crosley DR. 35.  1986. Quenching of OH (A2Σ+, v′ = 0) by H2, N2O, and hydrocarbons at elevated temperatures. J. Chem. Phys. 85:3896–901 [Google Scholar]
  36. Creasey DJ, Halford-Maw PA, Heard DE, Pilling MJ, Whitaker BJ. 36.  1997. Implementation and initial deployment of a field instrument for measurement of OH and HO2 in the troposphere by laser-induced fluorescence. J. Chem. Soc. Faraday Trans. 93:2907–13 [Google Scholar]
  37. Heal MR, Heard DE, Pilling MJ, Whitaker BJ. 37.  1995. On the development and validation of FAGE for local measurement of tropospheric OH and HO2. J. Atmos. Sci. 52:3428–41 [Google Scholar]
  38. Heard DE. 38.  2006. Atmospheric field measurements of the hydroxyl radical using laser-induced fluorescence spectroscopy. Annu. Rev. Phys. Chem. 57:191–216 [Google Scholar]
  39. Crosley DR. 39.  1989. Rotational and translation effects in collisions of electronically excited diatomic hydrides. J. Phys. Chem. 93:6273–82 [Google Scholar]
  40. Hemming BL, Crosley DR. 40.  2002. Rotational-level dependence of OH A2Σ+ quenching at 242 and 196 K. J. Phys. Chem. A 106:8992–95 [Google Scholar]
  41. Hemming BL, Crosley DR, Harrington JE, Sick V. 41.  2001. Collisional quenching of high rotational levels in A2Σ+ OH. J. Chem. Phys. 115:3099–104 [Google Scholar]
  42. Settersten TB, Patterson BD, Kronemayer H, Sick V, Schulz C, Daily JW. 42.  2006. Branching ratios for quenching of nitric oxide A2Σ+(v′ = 0) to X2Π(v″ = 0). Phys. Chem. Chem. Phys. 8:5328–38 [Google Scholar]
  43. Zare RN, Herschbach DR. 43.  1963. Doppler line shape of atomic fluorescence excited by molecular photodissociation. Proc. IEEE 51:173–82 [Google Scholar]
  44. Hancock G, Saunders M. 44.  2008. Vibrational distribution in NO(X2Π) formed by self quenching of NO A2Σ+ (v = 0). Phys. Chem. Chem. Phys. 10:2014–19 [Google Scholar]
  45. Paci MAB, Few J, Gowrie S, Hancock G. 45.  2013. Products of the quenching of NO A2Σ+(v = 0) by N2O and CO2. Phys. Chem. Chem. Phys. 15:2554–64 [Google Scholar]
  46. Estupiñán EG, Stickel RE, Wine PH. 46.  2001. An investigation of N2O production from quenching of OH(A2Σ+) by N2. Chem. Phys. Lett. 336:109–17 [Google Scholar]
  47. von Neumann J, Wigner E. 47.  1929. Uber das Verhalten von Eigenwerten bei adiabatischen Prozessen. Phys. Z. 30:467–70 [Google Scholar]
  48. Koppel H, Domcke W, Cederbaum LS. 48.  1984. Multimode molecular dynamics beyond the Born-Oppenheimer approximation. Adv. Chem. Phys. 57:59–246 [Google Scholar]
  49. Manaa MR, Yarkony DR. 49.  1994. On the role of conical intersections of two potential energy surfaces of the same symmetry in photodissociation. 2. CH3SCH3 → CH3S+CH3. J. Am. Chem. Soc. 116:11444–48 [Google Scholar]
  50. Yarkony DR. 50.  2001. Nuclear dynamics near conical intersections in the adiabatic representation: I. The effects of local topography on interstate transitions. J. Chem. Phys. 114:2601–13 [Google Scholar]
  51. Yarkony DR. 51.  1998. Conical intersections: diabolical and often misunderstood. Acc. Chem. Res. 31:511–18 [Google Scholar]
  52. Hernandez R, Clary DC. 52.  1995. Electronic spectra of the OH (A2Σ+)-H2 and OH(A2Σ+)-D2 complexes. Chem. Phys. Lett. 244:421–26 [Google Scholar]
  53. Miller SM, Clary DC, Kliesch A, Werner HJ. 53.  1994. Rotationally inelastic and bound state dynamics of H2-OH(X2Π). Mol. Phys. 83:405–28 [Google Scholar]
  54. Loomis RA, Lester MI. 54.  1995. Stabilization of reactants in a weakly-bound complex: OH-H2 and OH-D2. J. Chem. Phys. 103:4371–74 [Google Scholar]
  55. Loomis RA, Lester MI. 55.  1997. OH-H2 entrance channel complexes. Annu. Rev. Phys. Chem. 48:643–73 [Google Scholar]
  56. Loomis RA, Schwartz RL, Lester MI. 56.  1996. Electronic spectroscopy and quenching dynamics of OH-H2/D2 pre-reactive complexes. J. Chem. Phys. 104:6984–96 [Google Scholar]
  57. Yarkony DR. 57.  1996. Current issues in nonadiabatic chemistry. J. Phys. Chem. 100:18612–28 [Google Scholar]
  58. Yarkony DR. 58.  1999. Substituent effects and the noncrossing rule: the importance of reduced symmetry subspaces. I. The quenching of OH(A2Σ+) by H2. J. Chem. Phys. 111:6661–64 [Google Scholar]
  59. Vegiri A, Farantos SC. 59.  1988. Electronic deexcitation of OH(A2Σ+) with CO(X1Σ+): an ab initio study. Selectivity in Chemical Reactions JC Whitehead 393–402 Dordrecht: Kluwer Acad. [Google Scholar]
  60. Vegiri A, Farantos SC. 60.  1990. A classical dynamical investigation of the mechanism of electronic quenching of OH(A2Σ+) in collisions with CO(X1Σ+). Mol. Phys. 69:129–46 [Google Scholar]
  61. Bearpark MJ, Robb MA, Schlegel HB. 61.  1994. A direct method for the location of the lowest energy point on a potential surface crossing. Chem. Phys. Lett. 223:269–74 [Google Scholar]
  62. Hancock G. 62.  2013. Personal communication.
  63. Conte R, Fu B, Kamarchik E, Bowman JM. 63.  2013. A novel Gaussian binning (1GB) analysis of vibrational state distributions in highly excited H2O from reactive quenching of OH* by H2. J. Chem. Phys. 139:044104 [Google Scholar]
  64. Truhlar DG, Bowman JM. 64.  2013. Personal communication.
  65. Dillon J, Yarkony DR. 65.  2013. On the mechanism for the nonadiabatic reactive quenching of OH (A2Σ+) by H2 (1Σg+): the role of the 22A state. J. Chem. Phys. 139:064314 [Google Scholar]
/content/journals/10.1146/annurev-physchem-040513-103628
Loading
/content/journals/10.1146/annurev-physchem-040513-103628
Loading

Data & Media loading...

Supplemental Material

    Sample trajectory for the nonreactive quenching of OH 2Σ+ by H, initiated at a C conical intersection. The large degree of OH rotational excitation is seen, consistent with experimental results, as well as significant H vibration. Video 1 reprinted with permission from Reference 17. Copyright 2010, AIP Publishing LLC.

    Sample trajectory for the reactive quenching of OH 2Σ+ by H, showing an abstraction process initiated at a C conical intersection. The water product is shown to have significant vibrational excitation. Video 2 reprinted with permission from Reference 17. Copyright 2010, AIP Publishing LLC.

    Sample trajectory for the reactive quenching of OH 2Σ+ by H, showing an insertion process initiated at a C conical intersection. As with the abstraction channel, the water product is shown to have significant vibrational excitation. Video 3 reprinted with permission from Reference 17. Copyright 2010, AIP Publishing LLC.

  • Article Type: Review Article
This is a required field
Please enter a valid email address
Approval was a Success
Invalid data
An Error Occurred
Approval was partially successful, following selected items could not be processed due to error