Absorption and emission lineshapes and ultrafast solvation dynamics of NO in parahydrogen.

We perform a theoretical study on the electronic spectroscopy of dilute NO impurity embedded in parahydrogen (p-H(2)). Absorption and emission lineshapes for the A (2)Sigma(+)<--X (2)Pi Rydberg transition of NO in parahydrogen have been previously measured and simulated, which yielded results for the NO/p-H(2) ground and excited state pair potentials [L. Bonacina et al., J. Chem. Phys. 125, 054507 (2006)]. Using these potentials, we performed molecular dynamics simulation, theoretical statistical mechanical calculations of absorption and emission lineshapes, and both equilibrium and nonequilibrium solvation correlation functions for NO chromophore in parahydrogen. Theory was shown to be in good agreement with simulation. Linear response treatment of solvation dynamics was shown to break down due to a dramatic change in the solute-solvent microstructure upon solute excitation to the Rydberg state and the concomitant increase of the solute size.