In this study, thin films of pentaerythritol tetranitrate (PETN) were shock compressed using the laser driven shock apparatus at Los Alamos National Laboratory (LANL). Two spectroscopic probes were available to this apparatus: visible white light transient absorption spectroscopy (VIS) from 400 to 700 nm and mid-infrared transient absorption spectroscopy (MIR) from 1150 to 3800 cm–1. Important PETN vibrational modes are the symmetric and antisymmetric NO2 stretches at 1280 and 1650 cm–1, respectively, as well as CH stretches at ~2900 cm–1. Shock strength was varied from approximately 3 to 55 GPa to span from the chemically unreactive regime to the regime in which fast chemical reaction took place on the 250 ps time scale of the measurements. VIS and MIR results suggest irreversible chemistry was induced in PETN at pressures above 30 GPa. At lower shock pressures, the spectroscopy showed minimal changes attributable to pressure induced effects. Under the higher-pressure reactive conditions, the frequency region at the antisymmetric NO2 stretch mode had a significantly increased absorption while the region around the symmetric NO2 stretch did not. No observable increased absorption occurred in the higher frequency regions where CH-, NH-, and OH- bond absorptions would be observed. A broad absorption appeared on the shoulder at the red-edge of the CO2 vibrational band around 2200 cm–1. In addition to the experiments, reactive molecular dynamics were carried out under equivalent shock conditions to correlate the evolution of the infrared spectrum to molecular processes. The simulations show results consistent to experiments up to 30 GPa but suggest that NO and NO2 related features provided the strongest contributions to the shocked infrared changes. Proposed mechanisms for shocked PETN chemistry are analyzed as consistent or inconsistent with the data presented here. Our experimental data suggests C≡O or N2O bond formation, nitrite formation, and absence of significant hydroxyl or amine concentrations in the initial chemistry steps in PETN shocked above 30 GPa.
Powell, Michael Stephan, et al. "Insight into the Chemistry of PETN Under Shock Compression Through Ultrafast Broadband Mid-Infrared Absorption Spectroscopy." Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, vol. 124, no. 35, Aug. 2020. https://doi.org/10.1021/acs.jpca.0c03917
Powell, Michael Stephan, Sakano, Michael Neil, Cawkwell, Marc Jon, Bowlan, Pamela Renee, Brown, Kathryn Elizabeth, Bolme, Cynthia Anne, Moore, David Steven, Son, Steven F., Strachan, Alejandro, & Mcgrane, Shawn David (2020). Insight into the Chemistry of PETN Under Shock Compression Through Ultrafast Broadband Mid-Infrared Absorption Spectroscopy. Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, 124(35). https://doi.org/10.1021/acs.jpca.0c03917
Powell, Michael Stephan, Sakano, Michael Neil, Cawkwell, Marc Jon, et al., "Insight into the Chemistry of PETN Under Shock Compression Through Ultrafast Broadband Mid-Infrared Absorption Spectroscopy," Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 124, no. 35 (2020), https://doi.org/10.1021/acs.jpca.0c03917
@article{osti_1735915,
author = {Powell, Michael Stephan and Sakano, Michael Neil and Cawkwell, Marc Jon and Bowlan, Pamela Renee and Brown, Kathryn Elizabeth and Bolme, Cynthia Anne and Moore, David Steven and Son, Steven F. and Strachan, Alejandro and Mcgrane, Shawn David},
title = {Insight into the Chemistry of PETN Under Shock Compression Through Ultrafast Broadband Mid-Infrared Absorption Spectroscopy},
annote = {In this study, thin films of pentaerythritol tetranitrate (PETN) were shock compressed using the laser driven shock apparatus at Los Alamos National Laboratory (LANL). Two spectroscopic probes were available to this apparatus: visible white light transient absorption spectroscopy (VIS) from 400 to 700 nm and mid-infrared transient absorption spectroscopy (MIR) from 1150 to 3800 cm–1. Important PETN vibrational modes are the symmetric and antisymmetric NO2 stretches at 1280 and 1650 cm–1, respectively, as well as CH stretches at ~2900 cm–1. Shock strength was varied from approximately 3 to 55 GPa to span from the chemically unreactive regime to the regime in which fast chemical reaction took place on the 250 ps time scale of the measurements. VIS and MIR results suggest irreversible chemistry was induced in PETN at pressures above 30 GPa. At lower shock pressures, the spectroscopy showed minimal changes attributable to pressure induced effects. Under the higher-pressure reactive conditions, the frequency region at the antisymmetric NO2 stretch mode had a significantly increased absorption while the region around the symmetric NO2 stretch did not. No observable increased absorption occurred in the higher frequency regions where CH-, NH-, and OH- bond absorptions would be observed. A broad absorption appeared on the shoulder at the red-edge of the CO2 vibrational band around 2200 cm–1. In addition to the experiments, reactive molecular dynamics were carried out under equivalent shock conditions to correlate the evolution of the infrared spectrum to molecular processes. The simulations show results consistent to experiments up to 30 GPa but suggest that NO and NO2 related features provided the strongest contributions to the shocked infrared changes. Proposed mechanisms for shocked PETN chemistry are analyzed as consistent or inconsistent with the data presented here. Our experimental data suggests C≡O or N2O bond formation, nitrite formation, and absence of significant hydroxyl or amine concentrations in the initial chemistry steps in PETN shocked above 30 GPa.},
doi = {10.1021/acs.jpca.0c03917},
url = {https://www.osti.gov/biblio/1735915},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {ISSN 1089-5639},
number = {35},
volume = {124},
place = {United States},
publisher = {American Chemical Society},
year = {2020},
month = {08}}
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
89233218CNA000001
OSTI ID:
1735915
Report Number(s):
LA-UR--20-25037
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 35 Vol. 124; ISSN 1089-5639
SHOCK COMPRESSION OF CONDENSED MATTER - 2017: Proceedings of the Conference of the American Physical Society Topical Group on Shock Compression of Condensed Matter, AIP Conference Proceedingshttps://doi.org/10.1063/1.5044949
Proceedings of the conference of the American Physical Society topical group on shock compression of condensed matter, AIP Conference Proceedingshttps://doi.org/10.1063/1.50842
The tenth American Physical Society topical conference on shock compression of condensed matter, AIP Conference Proceedingshttps://doi.org/10.1063/1.55674
Journal Article
·
Sun May 01 00:00:00 EDT 1960
· Spectrochimica Acta (England) Divided into Spectrochim. Acta, Part A and Spectrochim. Acta, Part B
·OSTI ID:4166625