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164 records · Page 10

Quantum scattering of HC 5 N and para -H 2 on a new potential energy surface

In the interstellar medium (ISM), non-local thermodynamic equilibrium situations are common due to low density, and one needs to consider the effect of molecular collisions in order to interpret the observations. Among the species detected in the ISM, cyanopolyynes, with the general molecular formula HC 2n+1 N (n = 1, 2, …), are characterized by large dipole moments and small rotational constants and constitute an indispensable class of candidates for the sensitive tracers of local density and temperature. We present a study of the collisional (de-) excitation of HC 5 N by para -H 2 (p-H 2 ) in its ground rotational state, namely HC 5 N ( j 1 ) + H 2 ( j 2 = 0) → HC 5 N (j$_1^′$) + H2 (j$_2^′$ = 0), where j 1 (or j$_1^′$) and j 2 (or j$_2^′$) denote the initial (or final) rotational quantum numbers of HC 5 N and H 2 , respectively. We performed the quantum scattering calculations at low collision energy using a new four-dimensional ab initio potential energy surface. In the regime where p-H 2 remains in its rotational ground state, converged cross sections did not require including excited rotational states of p-H 2 in the rotational basis. State-to-state cross sections were computed by means of the quantum-mechanical close-coupling (CC) method and the coupled states (CS) approximation, and rate coefficients for the first 61 levels of HC 5 N were computed for the first time up to 20 K with the CC approach and up to 50 K with the CS method. CC and CS results were found to agree well at temperatures up to 20 K. Finally, these data should allow a more accurate derivation of the HC 5 N abundance in molecular clouds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shake-Down Spectroscopy as State- and Site-Specific Probe of Ultrafast Chemical Dynamics

Tracking the multifarious ultrafast electronic and structural changes occurring in a molecule during a photochemical transformation is a challenging endeavor that benefits from recent experimental and computational progress in time-resolved techniques. Measurements of valence electronic states, which provide a global picture of the bonding structure of the molecule, and core electronic states, which provide insight into the local environment, traditionally require different approaches and are often studied separately. Here, we demonstrate that X-ray pulses from a seeded free-electron laser (FEL) enable the measurement of high-resolution, time-resolved X-ray photoelectron spectra (XPS) that capture weak satellite states resulting from shake-down processes in a valence-excited molecule. This approach effectively combines the advantages of both valence- and core-state investigations. We applied this method to investigate photoexcited CS2 molecules, where the role of internal conversion (IC) and intersystem crossing (ISC) in determining the predissociation dynamics is controversial. We present XPS spectra from photoexcited CS2, obtained at the FERMI FEL. High-resolution measurements, compared to the corresponding spectra obtained from accurate multireference quantum chemical calculations, reveal that shake-down satellite channels are highly sensitive to both valence electronic and geometric changes. Previous studies of the predissociation dynamics have led to uncertain assignments of the branching between singlet and triplet excited states. We derive a propensity rule that demonstrates the spin-selectivity of the shake-downs. This selectivity allows us to unequivocally assign contributions from the bright and dark singlet excited states, with populations tracked along the predissociation dynamic pathway.

Thompson, Henry J. [Univ. of Southampton (United K↗