A parallel multistate framework for atomistic non-equilibrium reaction dynamics of solutes in strongly interacting organic solvents

We describe a parallel linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM. Forces are obtained using the Hellman-Feynmann relationship, giving continuous gradients, and excellent energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to CCSD(T)-F12 electronic structure theory, we built a 64-state MS-EVB model designed to study the F + CD3CN -> DF + CD2CN reaction in CD3CN solvent. This approach allows us to build a reactive potential energy surface (PES) whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We use our PES to run MD simulations, and examine a range of transient observables which follow in the wake of reaction, including transient spectra of the DF vibrational band, time dependent profiles of vibrationally excited DF in CD3CN solvent, and relaxation rates for energy flow from DF into the solvent, all of which agree well with experimental observations. Immediately following deuterium abstraction, the nascent DF is in a non-equilibrium regime in two different respects: (1) it is highly excited, with ~23 kcal mol-1 localized in the stretch; and (2) not yet Hydrogen bonded to the CD3CN solvent, its microsolvation environment is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral blue shift, while relaxation of its microsolvation environment results in a red shift. These two competing effects result in a post-reaction relaxation profile distinct from that observed when DF vibration excitation occurs within an equilibrium microsolvation environment. The parallel software framework presented in this paper should be more broadly applicable to a range of complex reactive systems.Comment: 58 pages and 29 Figure

Vibronic excitations of large molecules in solution studied by two-color pump–probe experiments on the 20 fs time scale

The ultrafast vibronic response of organic dye molecules in solution is studied in pump–probe experiments with 30 fs excitation pulses resonant to S0–Sn transitions. The molecular dynamics is probed either by pulses at the same spectral position or by 20 fs pulses overlapping with both the S0–S1 absorption and emission bands. Three contributions on distinctly different time scales are observed in the temporally and spectrally resolved two-color measurements. In the regime below 50 fs, a strong coherent coupling of the S0–Sn and the S0–S1 transitions occurs that is due to coherent vibrational motions in the electronic ground state. This signal is superimposed on the fast bleaching of the electronic ground state, resulting in a steplike increase of transmission. In the range of the S0–S1 emission band, one finds a subsequent picosecond rise of transmission that is due to stimulated emission from vibronic S1 states. The data demonstrate that the relaxation of Sn states directly populated by the pump pulses is much faster than the buildup of stimulated emission. This gives insight into different steps of intramolecular vibronic redistribution and is compared to the Sn–S1 relaxation in other molecules

Ultrafast spatio-temporal dynamics of terahertz generation by ionizing two-color femtosecond pulses in gases

We present a combined theoretical and experimental study of spatio-temporal propagation effects in terahertz (THz) generation in gases using two-color ionizing laser pulses. The observed strong broadening of the THz spectra with increasing gas pressure reveals the prominent role of spatio-temporal reshaping and of a plasma-induced blue-shift of the pump pulses in the generation process. Results obtained from (3+1)-dimensional simulations are in good agreement with experimental findings and clarify the mechanisms responsible for THz emission

Coherent oscillations of electrons in tunnel-coupled wells under ultrafast intersubband excitation

Ultrafast intersubband excitation of electrons in tunnell-coupled wells is studied depending on the structure parameters, the duration of the infrared pump and the detuning frequency. The temporal dependencies of the photoinduced concentration and dipole moment are obtained for two cases of transitions: from the single ground state to the tunnel-coupled excited states and from the tunnel-coupled states to the single excited state. The peculiarities of dephasing and population relaxation processes are also taken into account. The nonlinear regime of the response is also considered when the splitting energy between the tunnel-coupled levels is renormalized by the photoexcited electron concentration. The dependencies of the period and the amplitude of oscillations on the excitation pulse are presented with a description of the nonlinear oscillations damping.Comment: 8 pages, 12 figure

RdgB2 is required for dim-light input into intrinsically photosensitive retinal ganglion cells.

A subset of retinal ganglion cells is intrinsically photosensitive (ipRGCs) and contributes directly to the pupillary light reflex and circadian photoentrainment under bright-light conditions. ipRGCs are also indirectly activated by light through cellular circuits initiated in rods and cones. A mammalian homologue (RdgB2) of a phosphoinositide transfer/exchange protein that functions in Drosophila phototransduction is expressed in the retinal ganglion cell layer. This raised the possibility that RdgB2 might function in the intrinsic light response in ipRGCs, which depends on a cascade reminiscent of Drosophila phototransduction. Here we found that under high light intensities, RdgB2(-/-) mutant mice showed normal pupillary light responses and circadian photoentrainment. Consistent with this behavioral phenotype, the intrinsic light responses of ipRGCs in RdgB2(-/-) were indistinguishable from wild-type. In contrast, under low-light conditions, RdgB2(-/-) mutants displayed defects in both circadian photoentrainment and the pupillary light response. The RdgB2 protein was not expressed in ipRGCs but was in GABAergic amacrine cells, which provided inhibitory feedback onto bipolar cells. We propose that RdgB2 is required in a cellular circuit that transduces light input from rods to bipolar cells that are coupled to GABAergic amacrine cells and ultimately to ipRGCs, thereby enabling ipRGCs to respond to dim light

Time resolved X ray absorption spectroscopy of infrared laser induced temperature jumps in liquid water

A time resolved X ray absorption study of the structural dynamics of liquid water on a picosecond timescale is presented. We apply femtosecond midinfrared pulses to resonantly excite the intramolecular O H stretching band of liquid water and monitor the transient response in the oxygen K edge absorption spectrum with picosecond X ray pulses. In this way, structural changes in the hydrogen bond network of liquid water upon an ultrafast temperature jump of approximately 20 K are investigated. The changes of the X ray absorption as induced by such a temperature jump are about 3.2 . This demonstrates that our method serves as a sensitive probe of transient structural changes in liquid water and that combined infrared laser synchrotron experiments with substantially shorter X ray pulses, such as generated with a femtosecond slicing scheme, are possibl

Photophysics of closed- and open-ring isomers of a diarylethene with a carboxylic anchor group

We study the transient photophysical properties of a diarylethene with a carboxylic anchor group by a combination of steady-state and ultrafast emission and absorption spectroscopy. After excitation of the closed-ring form, fluorescence with a quantum yield of 10−5 is observed and separated into different spectro-temporal components. The S1 state of the closed-ring form shows a lifetime of 1.3 ps and decays mainly by internal conversion to the S0 state of this isomer. This vibrationally hot ground state cools on a time scale of 10 ps