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

Abstract

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 intomore » account whenever discussing the molecular photodynamics.« less

Authors:
 [1];  [2]
+ Show Author Affiliations
  1. Stony Brook Univ., NY (United States). Dept. of Chemistry
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1213379
Alternate Identifier(s):
OSTI ID: 1228703
Report Number(s):
BNL-108260-2015-JA
Journal ID: ISSN 0021-9606; JCPSA6; R&D Project: CO006; KC0301020; TRN: US1500643
Grant/Contract Number:  
SC0012704; AC02-98CH10886; SC00012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ionization; photons; excited states; absorption spectra; polycyclic aromatic hydrocarbons

Citation Formats

Johnson, Philip M., and Sears, Trevor J. Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers. United States: N. p., 2015. Web. doi:10.1063/1.4926925.
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Johnson, Philip M., & Sears, Trevor J. Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers. United States. https://doi.org/10.1063/1.4926925
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Johnson, Philip M., and Sears, Trevor J. Tue . "Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers". United States. https://doi.org/10.1063/1.4926925. https://www.osti.gov/servlets/purl/1213379.
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@article{osti_1213379,
title = {Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers},
author = {Johnson, Philip M. and Sears, Trevor J.},
abstractNote = {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.},
doi = {10.1063/1.4926925},
journal = {Journal of Chemical Physics},
number = 4,
volume = 143,
place = {United States},
year = {Tue Jul 28 00:00:00 EDT 2015},
month = {Tue Jul 28 00:00:00 EDT 2015}
}
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    Vibrationally assisted below-threshold ionization
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