TY  - JOUR
A1  - Banerjee, Shiladitya
A1  - Kröner, Dominik
A1  - Saalfrank, Peter
T1  - Resonance Raman and vibronic absorption spectra with Duschinsky rotation from a time-dependent perspective application to beta-carotene
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - The time-dependent approach to electronic spectroscopy, as popularized by Heller and co-workers in the 1980s, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption and resonance Raman spectra of beta-carotene, with and without a solvent. Two-state models, the harmonic and the Condon approximations are used in order to do so. A new code has been developed which includes excited state displacements, vibrational frequency shifts, and Duschinsky rotation, i.e., mode mixing, for both non-adiabatic spectroscopies. It is shown that Duschinsky rotation has a pronounced effect on the resonance Raman spectra of beta-carotene. In particular, it can explain a recently found anomalous behaviour of the so-called nu(1) peak in resonance Raman spectra [N. Tschirner, M. Schenderlein, K. Brose, E. Schlodder, M. A. Mroginski, C. Thomsen, and P. Hildebrandt, Phys. Chem. Chem. Phys. 11, 11471 (2009)], which shifts with the change in excitation wavelength.
Y1  - 2012
U6  - https://doi.org/10.1063/1.4748147
SN  - 0021-9606
VL  - 137
IS  - 22
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Mehdaoui, Imed
A1  - Kröner, Dominik
A1  - Pykavy, Mikhail
A1  - Freund, H.-J.
A1  - Klüner, Thorsten
T1  - Photo-induced desorption of NO from NiO(100): calculation of the four-dimensional potential energy surfaces and systematic wave packet studies
N2  - The velocity distributions of the laser-induced desorption of NO molecules from an epitaxially grown film of NiO(100) on Ni(100) have been studied [ Mull et al., J. Chem. Phys., 1992, 96, 7108]. A pronounced bimodality of velocity distributions has been found, where the NO molecules desorbing with higher velocities exhibit a coupling to the rotational quantum states J. In this article we present simulations of state resolved velocity distributions on a full ab initio level. As a basis for this quantum mechanical treatment a 4D potential energy surface (PES) was constructed for the electronic ground and a representative excited state, using a NiO5Mg1318+ cluster. The PESs of the electronic ground and an excited state were calculated at the CASPT2 and the configuration interaction (CI) level of theory, respectively. Multi-dimensional quantum wave packet simulations on these two surfaces were performed for different sets of degrees of freedom. Our key finding is that at least a 3D wave packet simulation, in which the desorption coordinate Z, polar angle theta and lateral coordinate X are included, is necessary to allow the simulation of experimental velocity distributions. Analysis of the wave packet dynamics demonstrates that essentially the lateral coordinate, which was neglected in previous studies [Kluner et al., Phys. Rev. Lett. 1998, 80, 5208], is responsible for the experimentally observed bimodality. An extensive analysis shows that the bimodality is due to a bifurcation of the wave packet on the excited state PES, where the motion of the molecule parallel to the surface plays a decisive role
Y1  - 2006
UR  - http://xlink.rsc.org/jumptojournal.cfm?journal_code=CP
U6  - https://doi.org/10.1039/B512778e
ER  -