Ultrafast Photodissociation Dynamics of Nitromethane

Nelson, Tammie Renee; Bjorgaard, Josiah August; Greenfield, Margo Torello; Bolme, Cindy; Brown, Katie; Mcgrane, Shawn David; Scharff, Robert Jason; Tretiak, Sergei

doi:10.1021/acs.jpca.5b09776

Title: Ultrafast Photodissociation Dynamics of Nitromethane

Journal Article · Wed Jan 06 00:00:00 EST 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5b09776· OSTI ID:1479945

^[1];

^[1]; Greenfield, Margo Torello ^[1]; Bolme, Cindy ^[1]; Brown, Katie ^[1];

^[1]; Scharff, Robert Jason ^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Nitromethane (NM), a high explosive (HE) with low sensitivity, is known to undergo photolysis upon ultraviolet (UV) irradiation. The optical transparency, homogeneity, and extensive study of NM make it an ideal system for studying photodissociation mechanisms in conventional HE materials. The photochemical processes involved in the decomposition of NM could be applied to the future design of controllable photoactive HE materials. In this work, the photodecomposition of NM from the nπ* state excited at 266 nm is being investigated on the femtosecond time scale. UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) are combined with nonadiabatic excited state molecular dynamics (NA-ESMD) simulations to provide a unified picture of NM photodecomposition. The FSRS spectrum of the photoproduct exhibits peaks in the NO₂ region and slightly shifted C–N vibrational peaks pointing to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of ~20 fs were predicted from NA-ESMD simulations. Predicted time scales revealed that NO₂ dissociation occurs in 81 ± 4 fs and methyl nitrite formation is much slower having a time scale of 452 ± 9 fs corresponding to the excited state absorption feature with a decay of 480 ± 17 fs observed in the TA spectrum. Lastly, although simulations predict C–N bond cleavage as the primary photochemical process, the relative time scales are consistent with isomerization occurring via NO₂ dissociation and subsequent rebinding of the methyl radical and nitrogen dioxide.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1479945

Report Number(s):: LA-UR-15-27850

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 4; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 36 works

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