Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers

Johnson, Philip M.; Sears, Trevor J.

doi:10.1063/1.4926925

Title: Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers

Journal Article · Tue Jul 28 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4926925· OSTI ID:1213379

Johnson, Philip M. ^[1]; Sears, Trevor J. ^[2]

Stony Brook Univ., NY (United States). Dept. of Chemistry
Stony Brook Univ., NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States)

Naphthalene, anthracene, and phenanthrene are shown to have very long-lived triplet lifetimes when the isolated molecules are excited with nanosecond pulsed lasers resonant with the lowest singlet state. For naphthalene, triplet state populations are created only during the laser pulse, excluding the possibility of normal intersystem crossing at the one photon level, and all molecules have triplet lifetimes greater than hundreds of microseconds, similar to the behavior previously reported for phenylacetylene. Although containing 7–12 thousand cm⁻¹ of vibrational energy, the triplet molecules have ionization thresholds appropriate to vibrationless T₁ states. The laser power dependences (slopes of log-log power plots) of the excited singlet and triplet populations are about 0.7 for naphthalene and about 0.5 for anthracene. Kinetic modeling of the power dependences successfully reproduces the experimental results and suggests that the triplet formation mechanism involves an enhanced spin orbit coupling caused by sigma character in states at the 2-photon level. Symmetry Adapted Cluster-Configuration Interaction calculations produced excited state absorption spectra to provide guidance for estimating kinetic rates and the sigma character present in higher electronic states. It is concluded that higher excited state populations are significant when larger molecules are excited with pulsed lasers and need to be taken into account whenever discussing the molecular photodynamics.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; AC02-98CH10886; SC00012704

OSTI ID:: 1213379

Alternate ID(s):: OSTI ID: 1228703

Report Number(s):: BNL-108260-2015-JA; JCPSA6; R&D Project: CO006; KC0301020; TRN: US1500643

Journal Information:: Journal of Chemical Physics, Vol. 143, Issue 4; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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References (60)

Nonradiative processes in the channel three region of the S1 state of ultracold benzene Otis, C. E.; Knee, J. L.; Johnson, P. M. The Journal of Physical Chemistry, Vol. 87, Issue 12 https://doi.org/10.1021/j100235a037	journal	June 1983
Spectroscopic studies on napththalene in the vapor phase. III. Phosphorescence and intersystem crossing yields of single vibronic levels Gattermann, H.; Stockburger, M. The Journal of Chemical Physics, Vol. 63, Issue 10 https://doi.org/10.1063/1.431134	journal	November 1975
Large, and irregular, inverse deuterium isotope effects on the singlet .fwdarw. triplet intersystem crossing of jet-cooled anthracenes Okajima, S.; Lim, E. C. The Journal of Physical Chemistry, Vol. 87, Issue 23 https://doi.org/10.1021/j100246a008	journal	November 1983
Rate equation modelling of molecular multiphoton ionization dynamics Zakheim, David S.; Johnson, Philip M. Chemical Physics, Vol. 46, Issue 3 https://doi.org/10.1016/0301-0104(80)85202-5	journal	March 1980
Two-Color Zero Kinetic Energy Photoelectron Spectra of Benzonitrile and Its van der Waals Complexes with Argon. Adiabatic Ionization Potentials and Cation Vibrational Frequencies Araki, Mitsunori; Sato, Shin-ichiro; Kimura, Katsumi The Journal of Physical Chemistry, Vol. 100, Issue 25 https://doi.org/10.1021/jp960565a	journal	January 1996
Extinction coefficients for triplet-triplet absorption in ethanol solutions of anthracene, naphthalene, 2,5-diphenyloxazole, 7-diethylamino- 4-methyl coumarin and 4-methyl-7-amino-carbostyril Dempster, D. N.; Morrow, T.; Quinn, M. F. Journal of Photochemistry, Vol. 2, Issue 5 https://doi.org/10.1016/0047-2670(73)80031-0	journal	January 1973
Spin-orbit coupling and intersystem crossing in molecules: Spin-orbit coupling Marian, Christel M. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.83	journal	July 2011
The energy of the lowest triplet state of gas phase benzene Sharpe, Steven; Johnson, Philip The Journal of Chemical Physics, Vol. 81, Issue 9 https://doi.org/10.1063/1.448130	journal	November 1984
The vacuum ultraviolet spectrum of naphthalene vapour for photon energies from 5 to 30 eV Koch, E. E.; Otto, A.; Radler, K. Chemical Physics Letters, Vol. 16, Issue 1 https://doi.org/10.1016/0009-2614(72)80474-3	journal	September 1972
Spin-orbit coupling in aromatic hydrocarbons. The radiative triplet lifetime of naphthalene R. Henry, Bryan; Siebrand, Willem Chemical Physics Letters, Vol. 3, Issue 9 https://doi.org/10.1016/0009-2614(69)87023-5	journal	September 1969
Calculations of the Lower Excited Levels of Benzene Roothaan, C. C. J.; Parr, Robert G. The Journal of Chemical Physics, Vol. 17, Issue 10 https://doi.org/10.1063/1.1747064	journal	October 1949
Fate of Excited States in Jet-Cooled Aromatic Molecules: Bifurcating Pathways and Very Long Lived Species from the S ₁ Excitation of Phenylacetylene and Benzonitrile Hofstein, Jason; Xu, Haifeng; Sears, Trevor The Journal of Physical Chemistry A, Vol. 112, Issue 6 https://doi.org/10.1021/jp077367b	journal	February 2008
Vibrational Analysis of Vacuum Ultraviolet Mass-Analyzed Threshold Ionization Spectra of Phenylacetylene and Benzonitrile Kwon, Chan Ho; Kim, Hong Lae; Kim, Myung Soo The Journal of Physical Chemistry A, Vol. 107, Issue 50 https://doi.org/10.1021/jp036391w	journal	December 2003
Competing ultrafast intersystem crossing and internal conversion in the “channel 3” region of benzene Minns, R. S.; Parker, D. S. N.; Penfold, T. J. Physical Chemistry Chemical Physics, Vol. 12, Issue 48 https://doi.org/10.1039/c001671c	journal	January 2010
Photodetachment photoelectron spectroscopy of mass selected anions: anthracene and the anthracene-H2O cluster Schiedt, J.; Weinkauf, R. Chemical Physics Letters, Vol. 266, Issue 1-2 https://doi.org/10.1016/S0009-2614(96)01512-6	journal	February 1997
Electron-energy-loss spectroscopy of solid phenylacetylene Swiderek, P.; Göötz, B.; Winterling, H. Chemical Physics Letters, Vol. 285, Issue 3-4 https://doi.org/10.1016/s0009-2614(98)00023-2	journal	March 1998
Molecular multiphoton ionization spectroscopy Johnson, Philip M. Applied Optics, Vol. 19, Issue 23 https://doi.org/10.1364/ao.19.003920	journal	January 1980
The effect of molecular distortions on spin–orbit coupling in simple hydrocarbons Penfold, T. J.; Worth, G. A. Chemical Physics, Vol. 375, Issue 1 https://doi.org/10.1016/j.chemphys.2010.07.019	journal	September 2010
Spin-orbit coupling in aromatic hydrocarbons. The radiative triplet lifetime of naphthalene Henry, Bryan R.; Siebrand, Willem Chemical Physics Letters, Vol. 3, Issue 2 https://doi.org/10.1016/0009-2614(69)80056-4	journal	February 1969
Phosphorescence spectra of benzonitrile and related compounds Takei, Kunio; Kanda, Yoshiya Spectrochimica Acta, Vol. 18, Issue 9 https://doi.org/10.1016/0371-1951(62)80150-7	journal	September 1962
Enhancement of Triplet Stability in Benzene by Substituents with Triple Bonds Johnson, Philip M.; Sears, Trevor J. The Journal of Physical Chemistry A, Vol. 117, Issue 33 https://doi.org/10.1021/jp403727f	journal	July 2013
The absorption spectrum of the anthracene molecule in the vacuum ultraviolet Koch, E. E.; Otto, A.; Radler, K. Chemical Physics Letters, Vol. 21, Issue 3 https://doi.org/10.1016/0009-2614(73)80293-3	journal	September 1973
The triplet–triplet absorption spectra of some aromatic hydrocarbons and related substances Craig, D. P.; Ross, I. G. J. Chem. Soc., Vol. 0, Issue 0 https://doi.org/10.1039/jr9540001589	journal	January 1954
Calculations of the Lower Excited Levels of Benzene Goeppert‐Mayer, M.; Sklar, A. L. The Journal of Chemical Physics, Vol. 6, Issue 10 https://doi.org/10.1063/1.1750138	journal	October 1938
Extinction coefficients and quantum yields for triplet—triplet absorption using laser flash photolysis Compton, R. H.; Grattan, K. T. V.; Morrow, T. Journal of Photochemistry, Vol. 14, Issue 1 https://doi.org/10.1016/0047-2670(80)85068-4	journal	January 1980
Vibronic coupling in the ground cationic state of naphthalene: A laser threshold photoelectron [zero kinetic energy (ZEKE)‐photoelectron] spectroscopic study Cockett, Martin C. R.; Ozeki, Hiroyuki; Okuyama, Katsuhiko The Journal of Chemical Physics, Vol. 98, Issue 10 https://doi.org/10.1063/1.464584	journal	May 1993
The energy gap law for radiationless transitions in large molecules Englman, Robert; Jortner, Joshua Molecular Physics, Vol. 18, Issue 2 https://doi.org/10.1080/00268977000100171	journal	February 1970
Structure and excited-state dynamics of anthracene: Ultrahigh-resolution spectroscopy and theoretical calculation Baba, Masaaki; Saitoh, Motohisa; Taguma, Kunio The Journal of Chemical Physics, Vol. 130, Issue 13 https://doi.org/10.1063/1.3104811	journal	April 2009
Electron-energy-loss spectroscopy of solid phenanthrene and biphenylene: Search for the low-lying triplet states Swiderek, Petra; Michaud, M.; Hohlneicher, G. Chemical Physics Letters, Vol. 178, Issue 2-3 https://doi.org/10.1016/0009-2614(91)87071-i	journal	March 1991
Vapor Absorption Spectra and Oscillator Strengths of Naphthalene, Anthracene, and Pyrene Ferguson, J.; Reeves, L. W.; Schneider, W. G. Canadian Journal of Chemistry, Vol. 35, Issue 10 https://doi.org/10.1139/v57-152	journal	October 1957
Ultrafast Dynamics in Superexcited States of Phenol Schick, Carolyn P.; Weber, Peter M. The Journal of Physical Chemistry A, Vol. 105, Issue 15 https://doi.org/10.1021/jp003303o	journal	April 2001
Vibrational spectroscopy of gas-phase neutral and cationic phenanthrene in their electronic groundstates (Hans) Piest, J. A.; Oomens, Jos; Bakker, Joost Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 57, Issue 4 https://doi.org/10.1016/s1386-1425(00)00439-x	journal	March 2001
Determination of the ionization energy of the benzene-argon complex by zero kinetic energy photoelectron spectroscopy Chewter, Leslie A.; Müller-Dethlefs, Klaus; Schlag, Edward W. Chemical Physics Letters, Vol. 135, Issue 3 https://doi.org/10.1016/0009-2614(87)85145-x	journal	April 1987
Vibronic activity in the laser jet spectra of phenanthrene Warren, Jonathan A.; Hayes, John M.; Small, Gerald J. Chemical Physics, Vol. 102, Issue 3 https://doi.org/10.1016/0301-0104(86)80005-2	journal	March 1986
Molecular Multiphoton Spectroscopy with Ionization Detection Johnson, P. M.; Otis, C. E. Annual Review of Physical Chemistry, Vol. 32, Issue 1 https://doi.org/10.1146/annurev.pc.32.100181.001035	journal	October 1981
Time evolution studies of triplet toluene by two‐color photoionization Dietz, T. G.; Duncan, M. A.; Smalley, R. E. The Journal of Chemical Physics, Vol. 76, Issue 3 https://doi.org/10.1063/1.443140	journal	February 1982
A study of anthracene–Ar _n ( n =0–5) in the ground cationic state by laser threshold photoelectron spectroscopy: Selective ionization of complex isomers formed in the free jet expansion Cockett, Martin C. R.; Kimura, Katsumi The Journal of Chemical Physics, Vol. 100, Issue 5 https://doi.org/10.1063/1.466386	journal	March 1994
Triplet state nonradiative lifetimes of collision‐free aniline and aniline–argon complexes above the S ₁ origin Knee, J. L.; Johnson, P. M. The Journal of Chemical Physics, Vol. 80, Issue 1 https://doi.org/10.1063/1.446497	journal	January 1984
Radiationless transitions in gas phase phenol and the effects of hydrogen bonding Sur, Abha; Johnson, Philip M. The Journal of Chemical Physics, Vol. 84, Issue 3 https://doi.org/10.1063/1.450512	journal	February 1986
The intensity of absorption of naphthalene from 30 000 cm−1 to 53 000 cm−1 George, G. A.; Morris, G. C. Journal of Molecular Spectroscopy, Vol. 26, Issue 1 https://doi.org/10.1016/0022-2852(68)90143-4	journal	May 1968
Ethynylbenzene analysis of the 2790 Å absorption system King, G. W.; So, S. P. Journal of Molecular Spectroscopy, Vol. 37, Issue 3 https://doi.org/10.1016/0022-2852(71)90183-4	journal	March 1971
Lifetimes of dissociation-relaxed triplet states of pyrazine and pyrimidine Knee, Joseph; Johnson, Philip The Journal of Physical Chemistry, Vol. 89, Issue 6 https://doi.org/10.1021/j100252a012	journal	March 1985
High-resolution spectroscopy of weak and short-lived bands of the S1 B13u←S0 A1g transition of naphthalene Yoshida, Kazuto; Semba, Yosuke; Kasahara, Shunji The Journal of Chemical Physics, Vol. 130, Issue 19 https://doi.org/10.1063/1.3122039	journal	May 2009
The Electronic Structure and Spectrum of Benzonitrile Peacock, T. E.; Wilkinson, P. T. Proceedings of the Physical Society, Vol. 79, Issue 1 https://doi.org/10.1088/0370-1328/79/1/315	journal	January 1962
The density of vibrational energy levels of polyatomic molecules Haarhoff, P. C. Molecular Physics, Vol. 7, Issue 2 https://doi.org/10.1080/00268976300100871	journal	January 1964
The Doppler-free two-photon absorption spectroscopy of naphthalene with Zeeman effects Okubo, Mitsushi; Misono, Masatoshi; Wang, Jinguo The Journal of Chemical Physics, Vol. 116, Issue 21 https://doi.org/10.1063/1.1473812	journal	June 2002
Response Theory Studies of Triplet-State Spectra and Radiative Lifetimes of Naphthalene, Quinoxaline, and Phthalazine Aagren, Hans; Minaev, Boris F.; Knuts, Soeren The Journal of Physical Chemistry, Vol. 98, Issue 15 https://doi.org/10.1021/j100066a007	journal	April 1994
Structure sensitive photoionization via Rydberg levels Kuthirummal, Narayanan; Weber, Peter M. Journal of Molecular Structure, Vol. 787, Issue 1-3 https://doi.org/10.1016/j.molstruc.2005.10.043	journal	April 2006
Pyrazine: An "Exact" Solution to the Problem of Radiationless Transitions Kommandeur, J.; Majewski, W. A.; Meerts, W. L. Annual Review of Physical Chemistry, Vol. 38, Issue 1 https://doi.org/10.1146/annurev.pc.38.100187.002245	journal	October 1987
Nonresonant multiphoton ionization spectroscopy: The four‐photon ionization spectrum of nitric oxide Johnson, Philip M.; Berman, Michael R.; Zakheim, David The Journal of Chemical Physics, Vol. 62, Issue 6 https://doi.org/10.1063/1.430732	journal	March 1975
Mass spectrometry of aromatic molecules with resonance-enhanced multiphoton ionization Lubman, David M.; Kronick, Mel N. Analytical Chemistry, Vol. 54, Issue 4 https://doi.org/10.1021/ac00241a014	journal	April 1982
Nonexponential decays in single vibronic level fluorescence: A comparison between kinetics and quantum mechanical treatment Lahmani, F.; Tramer, A.; Tric, C. The Journal of Chemical Physics, Vol. 60, Issue 11 https://doi.org/10.1063/1.1680921	journal	June 1974
Use of local modes in the description of highly vibrationally excited molecules Henry, Bryan R. Accounts of Chemical Research, Vol. 10, Issue 6 https://doi.org/10.1021/ar50114a003	journal	June 1977
Photoionization measurement of the triplet lifetime of benzene Duncan, M. A.; Dietz, T. G.; Liverman, M. G. The Journal of Physical Chemistry, Vol. 85, Issue 1 https://doi.org/10.1021/j150601a003	journal	January 1981
Pyrazine and pyrimidine triplet decay in a supersonic beam Dietz, T. G.; Duncan, M. A.; Puiu, A. C. The Journal of Physical Chemistry, Vol. 86, Issue 20 https://doi.org/10.1021/j100217a028	journal	September 1982
Ultrafast dynamics of the S1 excited state of benzene Parker, D. S. N.; Minns, R. S.; Penfold, T. J. Chemical Physics Letters, Vol. 469, Issue 1-3 https://doi.org/10.1016/j.cplett.2008.12.069	journal	February 2009
The ¹ B _{2 u} ←← ¹ A _{l g} two‐photon spectra of several isotopes of benzene by supersonic beam–multiphoton ionization spectroscopy Sur, Abha; Knee, Joseph; Johnson, Philip The Journal of Chemical Physics, Vol. 77, Issue 2 https://doi.org/10.1063/1.443878	journal	July 1982
Molecular multiphoton ionization spectroscopy Johnson, Philip M. Accounts of Chemical Research, Vol. 13, Issue 1 https://doi.org/10.1021/ar50145a004	journal	January 1980
Phosphorescence spectra of benzonitrile and related compounds Takei, K.; Kanda, Y. Spectrochimica Acta, Vol. 18, Issue 4 https://doi.org/10.1016/S0371-1951(62)80239-2	journal	January 1962
Sub-Doppler rotationally resolved spectroscopy of lower vibronic bands of benzene with Zeeman effects Doi, Atsushi; Kasahara, Shunji; Katô, Hajime The Journal of Chemical Physics, Vol. 120, Issue 14 https://doi.org/10.1063/1.1651479	journal	April 2004

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