Axial H-Bonding Solvent Controls Inhomogeneous Spectral Broadening, While Peripheral H-Bonding Solvent Controls Vibronic Broadening: Cresyl Violet in Methanol.

The dynamics of the nuclei of both a chromophore and its condensed-phase environment control many spectral features, including the vibronic and inhomogeneous broadening present in spectral line shapes. For the cresyl violet chromophore in methanol, we here analyze and isolate the effect of specific chromophore-solvent interactions on simulated spectral densities, reorganization energies, and linear absorption spectra. Employing both chromophore and its condensed-phase environment control many spectral features, including the vibronic and inhomogeneous broadening present in spectral line shapes. For the cresyl violet chromophore in methanol, we here analyze and isolate the effect of specific chromophore-solvent interactions on simulated spectral densities, reorganization energies, and linear absorption spectra. Employing both force field and ab initio molecular dynamics trajectories along with the inclusion of only certain solvent molecules in the excited-state calculations, we determine that the methanol molecules axial to the chromophore are responsible for the majority of inhomogeneous broadening, with a single methanol molecule that forms an axial hydrogen bond dominating the response. The strong peripheral hydrogen bonds do not contribute to spectral broadening, as they are very stable throughout the dynamics and do not lead to increased energy-gap fluctuations. We also find that treating the strong peripheral hydrogen bonds as molecular mechanical point charges during the molecular dynamics simulation underestimates the vibronic coupling. Including these peripheral hydrogen bonding methanol molecules in the quantum-mechanical region in a geometry optimization increases the vibronic coupling, suggesting that a more advanced treatment of these strongly interacting solvent molecules during the molecular dynamics trajectory may be necessary to capture the full vibronic spectral broadening.

Digital Waveform Technology and the Next Generation of Mass Spectrometers.

Ion traps and guides are integral parts of current commercial mass spectrometers. They are currently operated with sinusoidal waveform technology that has been developed over many years. Recently, digital waveform technology has begun to emerge and promises to supplant its older cousin because it presents new capabilities that result from the ability to instantaneously switch the frequency and duty cycle of the waveforms. This manuscript examines these capabilities and reveals their uses and effects on instrumentation. Graphical Abstract ᅟ.

The Importance of Research-A Student Perspective.

As students, we will focus on the importance of an objective ranking system, research, and mentorship to an applicant. We will address points raised in the (Behavior Analysis In Practice 8(1):7-15, 2015) article as well as debate the usefulness of proposed standards of objective ranking.