Comparative study of the dissociation of molecular ions promoted by sequential absorption of infrared photons
DOI:
https://doi.org/10.32480/rscp.2018-23-1.35-56Keywords:
molecular ions, dissociation, multiphoton excitationAbstract
The dissociation of gas-phase substituted acetophenone molecular ions promoted by infrared multiphoton excitation has been studied by Fourier Transform ion cyclotron resonance mass spectrometry to obtain thermochemical data. Two methods have been explored: 1) sequential photon absorption of the radiation emitted by hot tungsten filament, and 2) a CW CO2 laser. In the first case, pseudo activation energies were obtained from Arrhenius-type plots of the dissociation constant as a function of temperature. In the second method, the dissociation constant as a function of laser intensity provides an alternative way to establish the activation energies. Master equation calculations have been used to estimate the dissociation energies and the limitations of the methods are discussed.
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References
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2. Ervin KM. Experimental Techniques in Gas-Phase Ion Thermochemistry. Chem Rev. 2001;101(2):391-444.
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4. Mayer PM, Parkinson CJ, Smith DM, Radom L. An assessment of theoretical procedures for the calculationof reliable free radical thermochemistry: a recommended new procedure. J. Chem. Phys. 1998;108(2):604-615.
5. Collins EM, Sengupta A, AbuSalim DI, Raghavachari K. Accurate thermochemistry for organic cations via error cancellation using connectivity-based hierarchy. J. Phys. Chem. A. 2018;122(6):1807-1812.
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8. Dunbar RC. Kinetics of low-intensity infrared laser photodissociation. The thermal model and application of the Tolman theorem, J. Chem. Phys. 1991;95(4):2537-2548.
9. Uechi GT, Dunbar RC. The kinetics of infrared laser photodissociation on n-butylbenezene ions at low pressure. J. Chem Phys. 1992;96(12):8897-8905.
10. Dunbar RC, Zaniewski RC. Infrared multiphoton dissociation of styrene ion by low-power continuous CO2 laser irradiation. J. Chem Phys. 1992;96(7):5069-5075.
11. Freitas MA, Hendrickson CL, Marshall AG. Determination of relative order of activation energies for gas-phase ion unimolecular dissociation by infrared radiation for gaseous multiphoton energy transfer. J. Am. Chem. Soc. 2000;122(32):7768-7775.
12. Paech K, Jockusch RA, Williams ER. Slow infrared laser dissociation of molecules in the rapid energy exchange limit. J. Phys. Chem A. 2002;106(42):9761-9766.
13. Flora JW, Muddiman DC. Determination of the relative energies of activation for the dissociation of aromatic versus aliphatic phosphopetides by ESI-FT-ICR-MS and IRMPD. J. Am. Soc. Mass Spectrom. 2004;15(1):121-127.
14. Schaefer M, Drayss MK, Blunk D, Purcell JM, Hendrickson CL, Marshall AG, Mookherjee A, Armentrout PB. Kinetic determination of potassium affinities by IRMPD: elucidation of precursor ion structures. J. Phys. Chem. A. 2009;113(27);7779-7783.
15. Doussineau T, Rodolphe A, Santacreu M, Dugourd P. Pushing the limit of infrared multiphoton dissociation to megadalton-size DNA ions. J. Phys. Chem. Lett. 2012;3(16):2141- 2145.
16. Thölmann D, Tonner DS, McMahon TB. Spontaneous unimolecular dissociation of small cluster ions, (H3O+)Ln and Cl-(H2O)n (n = 2–4), under Fourier transform ion cyclotron resonance conditions. J. Phys. Chem. 1994;98(8):2002–2004.
17. Dunbar RC, McMahon TB, Thölmann D, Tonner DS, Salahub DR, Wei D. Zero- pressure thermal radiation induced dissociation (ZTRID) of gas-phase cluster ions: Comparison of theory and experiment for (H2O)2Cl- and (H2O)3Cl-. J. Am. Chem. Soc. 1995;117(51):12819-12825.
18. Dunbar RC, McMahon TB. Activation of unimolecular reactions by ambient blackbody radiation. Science. 1998;279(2):194-197.
19. Dunbar R. C. BIRD Blackbody infrared radiative dissociation: evolution, principles, and applications. Mass Spectrom Rev. 2004;23(2):127-158.
20. Stevens SM, Dunbar RC, Price WD, Sena M, Watson CH, Nichols LS, Riveros JM, Richardson DE, Eyler JR. Blackbody infared radiative dissociation of partially solvated mixed ligand Ru(II) complex ions. J. Phys. Chem. A. 2004;108(45):9892-9900.
21. Lin CY, Dunbar RC. Zero-pressure thermal-radiation-induced dissociation of tetraethylsilane cations. J. Phys.Chem. 1996;100(2):655-659.
22. Rodriguez-Cruz SE, Jockusch RA, Williams ER. Hydration energies of divalent metal ions, Ca2+(H2O)n (n = 5-7) and Ni2+(H2O)n (n = 6-8), obtained by blackbody infrared radiative dissociation. J. Am. Chem. Soc. 1998;120(23):5842-5843.
23. Jockusch RA, Lemoff AS, Williams ER. Effect of metal ion and water coordination on the structure of a gas-phase amino acid. J. Am. Chem. Soc. 2001;123(49):12255-12265.
24. Fox BS, Beyer MK, Achatz U, Joos S, Niedner-Schatteburg G, Bondybey VE. Precipitation Reactions in Water Clusters. J. Phys. Chem. A. 2000;104(6):1147-1151.
25. Fentabil MA, Daneshfar R, Kitova EN, KlassenJS. Blackbody infrared radiative dissociation of protonated oligosaccharides. J. Am. Soc. Mass Spectrom. 2011;22(12), 2171-2178. 27.
26. Wang W, Kitova EN, Sun J, KlassenJS. Blackbody infrared radiative dissociation of nonspecific protein-carbohydrate complexes produced by nanoelectrospray ionization: the nature of the noncovalent interactions. J. Am. Soc. Mass Spectrom. 2005;16(10),1583-1594.
27. Ge Y, Horn DM, McLafferty FW. Blackbody infrared radiative dissociation of larger (42 kDa) multiply charged proteins. Int. J. Mass Spectrom. 2001;210/211(1-3):203-214.
28. Balaj OP, Berg CB, Reitmeier SJ, Bondybey VE, Beyer MK. A novel design of a temperature-controlled FT-ICR cell for low-temperature black-body infrared radiative dissociation (BIRD) studies of hydrated ions. Int. J. Mass Spectrom. 2009;279(1):5-9.
29. Isolani PC, Kida-Tinone MC, Linnert HV, MenegonJJ, RiverosJM, Tiedemann PW, Franzin RM. Construção e desempenho de um espectrômetro de massas por transformada de Fourier. Quím. Nova. 1992;15(4):351-354.
30. Amster J. Fourier Transform Mass Spectrometry. J. Mass Spectrom. 1996;31(12):1325-1337.
31. Marshall AG, Hendrickson CL, Jackson GS. Fourier Transform ion cyclotron resonance mass spectrometry: a primer. Mass Spectrom Rev. 1998;17(1):1-35.
32. Sena M. Dissociação unimolecular induzida por radiação térmica (Tese de Doutorado), Instituto de Química da Universidade de São Paulo; 2000.
33. Sena M, Riveros JM. Thermal dissociation of acetophenone molecular ions activated by thermal radiation. J. Phys. Chem. A. 1997;101(24):4384-4391.
34. Forsythe WE. Temperature, brightness and efficiency of selected sources of light en International Critical Tables of Numerical Data, Physics, Chemistry and Technology, 5th edition. New York: MacGraw-Hill; 1933, 245-247.
35. Forsythe WE, Adaams EQ. Radiating Characteristics of Tungsten and Tungsten Lamps. J. Opt. Soc. Am. 1945;35(2):108-113.
36. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery JA, Stratmann RE, Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterskk JW, Petersson GA, Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, FoxDJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challacombe M, Gill PMW,Johnson BG, Chen W, Wong MW, Andres JL, Head-Gordon M, Replogle ES, Pople JA. Gaussian 98 (Revision A.2). Pittsburgh: Gaussian, Inc.; 1998.
37. Sena M, Riveros JM. Ring-hydrogen participation in the keto-enol isomerization of the acetophenone radical cation. Chem. Eur. J. 2000;6(5):785-793.
38. Marcinek A, Michalak J, Rogowski J, Tang W, Bally T, Gebicki J. Enolization in Radical Cations of o-Methylacetophenone and Related Species under Cryogenic Conditions J. Chem. Soc. Perkin Trans. 1992;2(8):1353.
39. Giroldo T, Riveros JM. Keto-enol isomerization of gas-phase 2´-methylacetophenone molecular ions probed by high-temperature near-blackbody-induced dissociation, ion-molecule reactions, and ab initio calculations. J. Phys. Chem. A. 2002;106(42):9930-9938.
40. Bomse DS; Woodin RL, Beauchamp JL. Molecular activation with low-intensity CW infrared laser radiation. Multiphoton dissociation of ions derived from diethyl ether. J. Am. Chem. Soc. 1979;101(19):5503-5512.
41. Tolman RC. Statistical mechanics applied to chemistry. J. Am. Chem. Soc. 1920;42(12):2506-2528.
42. Rafatijo H, Thompson DL. General application of Tolman´s concept of activation energy. J. Chem. Phys. 2017;147(22):224111/1-224111/8.
43. Dunbar, R. C. Kinetics of thermal unimolecular dissociation by ambient infrared radiation. J. Phys. Chem. 1994, 98(15), 8705-8712.
44. Miller JA; Klippenstein SJ. The master equation in chemical kinetics. J. Phys. Chem. A. 2006;110(36):10528-10544.
45. Shannon R, Glowacki DR. A simple “boxed molecular kinetics” approach to accelerate rare events in the stochastic kinetic master equation. J. Phys. Chem. A. 2018;122(6):1531-1541.
46. Wong RL, Robinson EW, Williams ER. Activation of protonated peptides and molecular ions of small molecules using heated filaments in Fourier-transform ion cyclotron resonance mass spectrometry. Int. J. Mass Spectrom. 2004;234(1):1-9.
47. Huang Y, Peterman S, Tichy SE, North SW, Russell DH. Unimolecular dissociation reactions of methyl benzoate radical cation. J, Phys. Chem. A. 2008;112(46):11590-11597.
48. Mayer PM, Parkinson CJ, Smith DM, Radom L. An assessment of theoretical procedures for the calculation of reliable free radical thermochemistry: a recommended new procedure. J. Chem. Phys. 1998;108(2):604-615.
49. Froese RDJ, Morokuma K. IMOMO-G2MS approaches to accurate calculations of bond dissociation energies of large molecules. J. Phys. Chem. A. 1999;103(23):4580-4586.
50. Baer T, Dutuit O, Mestdagh H, Rolando C. Dissociation dynamics of n-butylbenzene ions: the competitive production of m/z 91 and 92 fragment ions. J. Phys. Chem.
51. Halbert S, Bouchoux G. Isomerization and dissociation of n-butylbenzene radical cations. J. Phys. Chem. A. 2012;116(4):1307-1315.
2. Ervin KM. Experimental Techniques in Gas-Phase Ion Thermochemistry. Chem Rev. 2001;101(2):391-444.
3. Wesdemiotis C, Wang P. Thermochemistry of biomolecules. Laskin J, Lifshitz C, editors. Principles of Mass Spectrometry Applied to Biomolecules. Hoboken, NJ: Wiley & Sons, 2006, p 565-617.
4. Mayer PM, Parkinson CJ, Smith DM, Radom L. An assessment of theoretical procedures for the calculationof reliable free radical thermochemistry: a recommended new procedure. J. Chem. Phys. 1998;108(2):604-615.
5. Collins EM, Sengupta A, AbuSalim DI, Raghavachari K. Accurate thermochemistry for organic cations via error cancellation using connectivity-based hierarchy. J. Phys. Chem. A. 2018;122(6):1807-1812.
6. Polfer NC. Infrared multiphoton spectroscopy of trapped ions. Chem. Soc. Rev. 2011;40(5):2211-2221.
7. Brodbelt J. Infrared multiphoton dissociation in quadrupole ion traps. Mass Spectrom. Rev. 2009;28(3):390-424.
8. Dunbar RC. Kinetics of low-intensity infrared laser photodissociation. The thermal model and application of the Tolman theorem, J. Chem. Phys. 1991;95(4):2537-2548.
9. Uechi GT, Dunbar RC. The kinetics of infrared laser photodissociation on n-butylbenezene ions at low pressure. J. Chem Phys. 1992;96(12):8897-8905.
10. Dunbar RC, Zaniewski RC. Infrared multiphoton dissociation of styrene ion by low-power continuous CO2 laser irradiation. J. Chem Phys. 1992;96(7):5069-5075.
11. Freitas MA, Hendrickson CL, Marshall AG. Determination of relative order of activation energies for gas-phase ion unimolecular dissociation by infrared radiation for gaseous multiphoton energy transfer. J. Am. Chem. Soc. 2000;122(32):7768-7775.
12. Paech K, Jockusch RA, Williams ER. Slow infrared laser dissociation of molecules in the rapid energy exchange limit. J. Phys. Chem A. 2002;106(42):9761-9766.
13. Flora JW, Muddiman DC. Determination of the relative energies of activation for the dissociation of aromatic versus aliphatic phosphopetides by ESI-FT-ICR-MS and IRMPD. J. Am. Soc. Mass Spectrom. 2004;15(1):121-127.
14. Schaefer M, Drayss MK, Blunk D, Purcell JM, Hendrickson CL, Marshall AG, Mookherjee A, Armentrout PB. Kinetic determination of potassium affinities by IRMPD: elucidation of precursor ion structures. J. Phys. Chem. A. 2009;113(27);7779-7783.
15. Doussineau T, Rodolphe A, Santacreu M, Dugourd P. Pushing the limit of infrared multiphoton dissociation to megadalton-size DNA ions. J. Phys. Chem. Lett. 2012;3(16):2141- 2145.
16. Thölmann D, Tonner DS, McMahon TB. Spontaneous unimolecular dissociation of small cluster ions, (H3O+)Ln and Cl-(H2O)n (n = 2–4), under Fourier transform ion cyclotron resonance conditions. J. Phys. Chem. 1994;98(8):2002–2004.
17. Dunbar RC, McMahon TB, Thölmann D, Tonner DS, Salahub DR, Wei D. Zero- pressure thermal radiation induced dissociation (ZTRID) of gas-phase cluster ions: Comparison of theory and experiment for (H2O)2Cl- and (H2O)3Cl-. J. Am. Chem. Soc. 1995;117(51):12819-12825.
18. Dunbar RC, McMahon TB. Activation of unimolecular reactions by ambient blackbody radiation. Science. 1998;279(2):194-197.
19. Dunbar R. C. BIRD Blackbody infrared radiative dissociation: evolution, principles, and applications. Mass Spectrom Rev. 2004;23(2):127-158.
20. Stevens SM, Dunbar RC, Price WD, Sena M, Watson CH, Nichols LS, Riveros JM, Richardson DE, Eyler JR. Blackbody infared radiative dissociation of partially solvated mixed ligand Ru(II) complex ions. J. Phys. Chem. A. 2004;108(45):9892-9900.
21. Lin CY, Dunbar RC. Zero-pressure thermal-radiation-induced dissociation of tetraethylsilane cations. J. Phys.Chem. 1996;100(2):655-659.
22. Rodriguez-Cruz SE, Jockusch RA, Williams ER. Hydration energies of divalent metal ions, Ca2+(H2O)n (n = 5-7) and Ni2+(H2O)n (n = 6-8), obtained by blackbody infrared radiative dissociation. J. Am. Chem. Soc. 1998;120(23):5842-5843.
23. Jockusch RA, Lemoff AS, Williams ER. Effect of metal ion and water coordination on the structure of a gas-phase amino acid. J. Am. Chem. Soc. 2001;123(49):12255-12265.
24. Fox BS, Beyer MK, Achatz U, Joos S, Niedner-Schatteburg G, Bondybey VE. Precipitation Reactions in Water Clusters. J. Phys. Chem. A. 2000;104(6):1147-1151.
25. Fentabil MA, Daneshfar R, Kitova EN, KlassenJS. Blackbody infrared radiative dissociation of protonated oligosaccharides. J. Am. Soc. Mass Spectrom. 2011;22(12), 2171-2178. 27.
26. Wang W, Kitova EN, Sun J, KlassenJS. Blackbody infrared radiative dissociation of nonspecific protein-carbohydrate complexes produced by nanoelectrospray ionization: the nature of the noncovalent interactions. J. Am. Soc. Mass Spectrom. 2005;16(10),1583-1594.
27. Ge Y, Horn DM, McLafferty FW. Blackbody infrared radiative dissociation of larger (42 kDa) multiply charged proteins. Int. J. Mass Spectrom. 2001;210/211(1-3):203-214.
28. Balaj OP, Berg CB, Reitmeier SJ, Bondybey VE, Beyer MK. A novel design of a temperature-controlled FT-ICR cell for low-temperature black-body infrared radiative dissociation (BIRD) studies of hydrated ions. Int. J. Mass Spectrom. 2009;279(1):5-9.
29. Isolani PC, Kida-Tinone MC, Linnert HV, MenegonJJ, RiverosJM, Tiedemann PW, Franzin RM. Construção e desempenho de um espectrômetro de massas por transformada de Fourier. Quím. Nova. 1992;15(4):351-354.
30. Amster J. Fourier Transform Mass Spectrometry. J. Mass Spectrom. 1996;31(12):1325-1337.
31. Marshall AG, Hendrickson CL, Jackson GS. Fourier Transform ion cyclotron resonance mass spectrometry: a primer. Mass Spectrom Rev. 1998;17(1):1-35.
32. Sena M. Dissociação unimolecular induzida por radiação térmica (Tese de Doutorado), Instituto de Química da Universidade de São Paulo; 2000.
33. Sena M, Riveros JM. Thermal dissociation of acetophenone molecular ions activated by thermal radiation. J. Phys. Chem. A. 1997;101(24):4384-4391.
34. Forsythe WE. Temperature, brightness and efficiency of selected sources of light en International Critical Tables of Numerical Data, Physics, Chemistry and Technology, 5th edition. New York: MacGraw-Hill; 1933, 245-247.
35. Forsythe WE, Adaams EQ. Radiating Characteristics of Tungsten and Tungsten Lamps. J. Opt. Soc. Am. 1945;35(2):108-113.
36. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery JA, Stratmann RE, Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterskk JW, Petersson GA, Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, FoxDJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challacombe M, Gill PMW,Johnson BG, Chen W, Wong MW, Andres JL, Head-Gordon M, Replogle ES, Pople JA. Gaussian 98 (Revision A.2). Pittsburgh: Gaussian, Inc.; 1998.
37. Sena M, Riveros JM. Ring-hydrogen participation in the keto-enol isomerization of the acetophenone radical cation. Chem. Eur. J. 2000;6(5):785-793.
38. Marcinek A, Michalak J, Rogowski J, Tang W, Bally T, Gebicki J. Enolization in Radical Cations of o-Methylacetophenone and Related Species under Cryogenic Conditions J. Chem. Soc. Perkin Trans. 1992;2(8):1353.
39. Giroldo T, Riveros JM. Keto-enol isomerization of gas-phase 2´-methylacetophenone molecular ions probed by high-temperature near-blackbody-induced dissociation, ion-molecule reactions, and ab initio calculations. J. Phys. Chem. A. 2002;106(42):9930-9938.
40. Bomse DS; Woodin RL, Beauchamp JL. Molecular activation with low-intensity CW infrared laser radiation. Multiphoton dissociation of ions derived from diethyl ether. J. Am. Chem. Soc. 1979;101(19):5503-5512.
41. Tolman RC. Statistical mechanics applied to chemistry. J. Am. Chem. Soc. 1920;42(12):2506-2528.
42. Rafatijo H, Thompson DL. General application of Tolman´s concept of activation energy. J. Chem. Phys. 2017;147(22):224111/1-224111/8.
43. Dunbar, R. C. Kinetics of thermal unimolecular dissociation by ambient infrared radiation. J. Phys. Chem. 1994, 98(15), 8705-8712.
44. Miller JA; Klippenstein SJ. The master equation in chemical kinetics. J. Phys. Chem. A. 2006;110(36):10528-10544.
45. Shannon R, Glowacki DR. A simple “boxed molecular kinetics” approach to accelerate rare events in the stochastic kinetic master equation. J. Phys. Chem. A. 2018;122(6):1531-1541.
46. Wong RL, Robinson EW, Williams ER. Activation of protonated peptides and molecular ions of small molecules using heated filaments in Fourier-transform ion cyclotron resonance mass spectrometry. Int. J. Mass Spectrom. 2004;234(1):1-9.
47. Huang Y, Peterman S, Tichy SE, North SW, Russell DH. Unimolecular dissociation reactions of methyl benzoate radical cation. J, Phys. Chem. A. 2008;112(46):11590-11597.
48. Mayer PM, Parkinson CJ, Smith DM, Radom L. An assessment of theoretical procedures for the calculation of reliable free radical thermochemistry: a recommended new procedure. J. Chem. Phys. 1998;108(2):604-615.
49. Froese RDJ, Morokuma K. IMOMO-G2MS approaches to accurate calculations of bond dissociation energies of large molecules. J. Phys. Chem. A. 1999;103(23):4580-4586.
50. Baer T, Dutuit O, Mestdagh H, Rolando C. Dissociation dynamics of n-butylbenzene ions: the competitive production of m/z 91 and 92 fragment ions. J. Phys. Chem.
51. Halbert S, Bouchoux G. Isomerization and dissociation of n-butylbenzene radical cations. J. Phys. Chem. A. 2012;116(4):1307-1315.
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Comparative study of the dissociation of molecular ions promoted by sequential absorption of infrared photons. Rev. Soc. cient. Py. [Internet]. 2018 Oct. 13 [cited 2026 May 13];23(1):35-56. Available from: https://sociedadcientifica.org.py/ojs/index.php/rscpy/article/view/34
