A quantum mechanics/molecular mechanics (QM/MM) type of scheme is employed to calculate the solventinduced shifts of molecular electronic excitations. The effective fragment potential (EFP) method was used for the classical potential. Since EFP has a density dependent functional form, in contrast with most other MM potentials, time-dependent density functional theory (TDDFT) has been modified to combine TDDFT with EFP. This new method is then used to perform a hybrid QM/MM molecular dynamics simulation to generate a simulated spectrum of the n→π * vertical excitation energy of acetone in vacuum and with 100 water molecules. The calculated watersolvent effect on the vertical excitation energy exhibits a blueshift of the n→π * vertical excitation energy in acetone (Δω1=0.211 eV), which is in good agreement with the experimental blueshift. KeywordsExcitation energies, Solvents, Density functional theory, Blue shift, Optical properties A quantum mechanics/molecular mechanics ͑QM/MM͒ type of scheme is employed to calculate the solvent-induced shifts of molecular electronic excitations. The effective fragment potential ͑EFP͒ method was used for the classical potential. Since EFP has a density dependent functional form, in contrast with most other MM potentials, time-dependent density functional theory ͑TDDFT͒ has been modified to combine TDDFT with EFP. This new method is then used to perform a hybrid QM/MM molecular dynamics simulation to generate a simulated spectrum of the n → ‫ء‬ vertical excitation energy of acetone in vacuum and with 100 water molecules. The calculated water solvent effect on the vertical excitation energy exhibits a blueshift of the n → ‫ء‬ vertical excitation energy in acetone ͑⌬ 1 = 0.211 eV͒, which is in good agreement with the experimental blueshift.

The energetics, interfacial properties, instabilities, and fragmentation patterns of electrosprays made from formamide salt solutions are investigated in a mass spectrometric vacuum electrospray experiment and using molecular dynamics (MD) simulations. The electrospray source is operated in a Taylor cone-jet mode, with the nanojet that forms being characterized by high surface-normal electric field strengths in the vicinity of 1 V/nm. Mass-to-charge ratios were determined for both positive and negative currents sprayed from NaI−formamide solutions with solute−solvent mole ratios of 1:8.4 and 1:36.9, and from KI−formamide solutions with mole ratios of 1:41 and 1:83. The molecular dynamics simulations were conducted on isolated 10 nm NaI−formamide droplets at mole ratios of 1:8 and 1:16. The droplet was subjected to a uniform electric field with strengths ranging between 0.5 and 1.5 V/nm. Both the experiments and simulations demonstrate a mixed charge emission regime where field-induced desorption of solvated ions and charged droplets occurs. The macroscopic parameters, such as average mass-to-charge ratio and maximum surface-normal field strengths deduced from the simulations are found to be in good agreement with the experimental work and consistent with electrohydrodynamic theory of cone-jets. The observed mass spectrometric Na+ and I− solvated ion distributions are consistent with a thermal evaporation process, and are correctly reproduced by the simulation after incorporation of the different flight times and unimolecular ion dissociation rates in the analysis. Alignment of formamide dipoles and field-induced reorganization of the positive and negative ionic charges in the interfacial region are both found to contribute to the surface-normal field near the points of charge emission. In the simulations the majority of cluster ions are found to be emitted from the tip of the jet rather than from the neck region next to the Taylor cone. This finding is consistent with the experimental energy distributions of the solvated ions which demonstrate that indeed most ions are emitted closer to the jet region, that is, beyond the cone-neck region where ohmic losses occur. This observation is also consistent with continuum electrohydrodynamic predictions of cluster-ion evaporation at surface regions of high curvature and therefore maximum surface electric field strengths, which may be the cone-neck region, the breakup region of the jet (usually near the tip of the jet), or the emitted charged droplets. In the nanoscale jets observed in this study, the regions of highest spatial curvature are at the ends of the jets where nascent drops either are forming or have just detached. The energetics, interfacial properties, instabilities, and fragmentation patterns of electrosprays made from formamide salt solutions are investigated in a mass spectrometric vacuum electrospray experiment and using molecular dynamics (MD) simulations. The electrospray source is operated in a Taylor cone-jet mode, with the nanojet that form...

The combined time-dependent density functional theory effective fragment potential method (TDDFT/EFP1) is applied to a study of the solvent-induced shift of the lowest singlet π → π* charge-transfer excited state of p-nitroaniline (pNA) from the gas to the condensed phase in water. Molecular dynamics simulations of pNA with 150 EFP1 water molecules are used to model the condensed-phase and generate a simulated spectrum of the lowest singlet charge-transfer excitation. The TDDFT/EFP1 method successfully reproduces the experimental condensed-phase π → π* vertical excitation energy and solvent-induced red shift of pNA in water. The largest contribution to the red shift comes from Coulomb interactions, between pNA and water, and solute relaxation. The solvent shift contributions reflect the increase in zwitterionic character of pNA upon solvation.