Dissociative electron attachment to amide bond containing molecules: N-ethylformamide and N-ethylacetamide.

To advance our quest to understand the role of low energy electrons in biomolecular systems, we performed investigations on dissociative electron attachment (DEA) to gas-phase N-ethylformamide (NEF) and N-ethylacetamide (NEA) molecules. Both molecules contain the amide bond, which is the linkage between two consecutive amino acid residues in proteins. Thus, their electron-induced dissociation can imitate the resonant behavior of the DEA process in more complex biostructures. Our experimental results indicate that in these two molecules, the dissociation of the amide bond results in a double resonant structure with peaks at ∼5 eV and 9 eV. We also determined the energy position of resonant states for several negative ions, i.e., the other dissociation products from NEF and NEA. Our predictions of dissociation channels were supported by density functional theory calculations of the corresponding threshold energies. Our results and those previously reported for small amides and peptides imply the fundamental nature for breakage of the amide bond through the DEA process.

Molecular Investigation of Contact Line Movement in Electrowetted Nanodroplets.

Molecular dynamics (MD) simulation of an electrowetted nanodroplet is performed to understand the fundamental origin of the involved parameters resulted from the molecular movement in the vicinity of the three-phase contact line (TPCL). During the spreading of the droplet, contact line friction (CLF) force is found to be the controlling one among all other resistive forces. Being molecular in nature, MD study is required to unveil the CLF, which is manifested by the TPCL friction coefficient ζ. The combined effect of temperature, electric field, and surface wettability, manifested by the solid-liquid Lennard-Jones interaction parameter, is studied to explore the droplet spreading. The entire droplet wetting dynamics is divided into two different regimes, namely, spreading regime and equilibrium regime. The molecular frequency during the TPCL movement in the equilibrium regime is affected by the presence of any external perturbation and results in an alteration of ζ. The predetermined knowledge of the alteration of CLF due to the coupling effect of electric field and temperature will have a potential application towards designing electric field-inspired droplet movement devices.

Dissociation dynamics in low energy electron attachment to ammonia using velocity slice imaging.

The complete dissociation dynamics of low energy electron attachment to the ammonia molecule has been studied using velocity slice imaging (VSI) spectrometry. One low energy resonant peak around 5.5 eV and a broad resonance around 10.5 eV incident electron energies have been observed. The resonant states mainly dissociate via H- and NH2- fragments, though for the upper resonant state, the signature of NH- fragments is also predicted due to a three-body dissociation process. Kinetic energy and angular distributions of the NH2- fragment anions are measured simultaneously around the two resonances. Based on our experimental observations, we conclude that a temporary negative ion (TNI) state with A1 symmetry is responsible for the lower resonance. Whereas, we find strong evidence for the existence of a TNI state having A1 symmetry at the 10.5 eV resonance for the first time.

A new time of flight mass spectrometer for absolute dissociative electron attachment cross-section measurements in gas phase.

A new time of flight mass spectrometer (TOFMS) has been developed to study the absolute dissociative electron attachment (DEA) cross section using a relative flow technique of a wide variety of molecules in gas phase, ranging from simple diatomic to complex biomolecules. Unlike the Wiley-McLaren type TOFMS, here the total ion collection condition has been achieved without compromising the mass resolution by introducing a field free drift region after the lensing arrangement. The field free interaction region is provided for low energy electron molecule collision studies. The spectrometer can be used to study a wide range of masses (H- ion to few hundreds atomic mass unit). The mass resolution capability of the spectrometer has been checked experimentally by measuring the mass spectra of fragment anions arising from DEA to methanol. Overall performance of the spectrometer has been tested by measuring the absolute DEA cross section of the ground state SO2 molecule, and the results are satisfactory.

Dipolar dissociation dynamics in electron collisions with carbon monoxide.

Dipolar dissociation processes in the electron collisions with carbon monoxide have been studied using time of flight (TOF) mass spectroscopy in combination with the highly differential velocity slice imaging (VSI) technique. By probing ion-pair states, both positive and/or negative ions may be detected. The ion yield curve of negative ions provides the threshold energy for the ion-pair production. On the other hand, the kinetic energy distributions and angular distributions of the fragment anion provide detailed dynamics of the dipolar dissociation process. Two ion-pair states have been identified based on angular distribution measurements using the VSI technique.