Journal of Physical Chemistry A, Vol.121, No.26, 4968-4981, 2017
Photoinitiated Dynamics in Amorphous Solid Water via Nanoimprint Lithography
Laser pulses that act on fragile samples often alter them irreversibly, motivating single-pulse data collection. Amorphous solid water (ASW) is a good example. In addition, neither well-defined paths for molecules to travel through ASW nor sufficiently small samples to enable molecular dynamics modeling have been achieved. Combining nanoimprint lithography and photoinitiation overcomes these obstacles. An array of gold nanopartides absorbs pulsed (10 us) 532 urn radiation and converts it to heat, and doped ASW films grown at about 100 K are ejected from atop the irradiated nanoparticles into vacuum. The nanopartides are spaced from one another by sufficient distance that each acts independently. Thus, a temporal profile of ejected material is the sum of about 10(6) "nanoexperiments," yielding high single-pulse signal-to-noise ratios. The size of a single nanopartide and its immediate surroundings is sufficiently small to enable modeling and simulation at the atomistic (molecular) level, which has not been feasible previously. An application to a chemical system is presented in which H/D scrambling is used to infer the presence of protons in films composed of D2O and H2O (each containing a small amount of HDO contaminant) upon which a small amount of NO2 has been deposited. The pulsed laser heating of the nanopartides promotes NO2/N2O4 hydrolysis to nitric acid, whose protons enhance H/D scrambling dramatically.