Previous works have shown that dressing of diatomic molecules by standing or by running laser waves gives rise to the appearance of so-called light-induced conical intersections (LICIs). Because of the strong nonadiabatic couplings, the existence of such LICIs may significantly change the dynamical properties of a molecular system. In our former paper (J. Phys. Chem. A 2013, 117, 8528), the photodissociation dynamics of the D(2)(+) molecule were studied in the LICI framework starting the initial vibrational nuclear wave packet from the superposition of all the vibrational states initially produced by ionizing D(2). The present work complements our previous investigation by letting the initial nuclear wave packets start from different individual vibrational levels of D(2)(+), in particular, above the energy of the LICI. The kinetic energy release spectra, the total dissociation probabilities, and the angular distributions of the photofragments are calculated and discussed. An interesting phenomenon has been found in the spectra of the photofragments. Applying the light-induced adiabatic picture supported by LICI, explanations are given for the unexpected structure of the spectra.
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http://dx.doi.org/10.1021/jp504889e | DOI Listing |
J Chem Theory Comput
January 2025
Department of Theoretical Physics, University of Debrecen, P.O. Box 400, Debrecen H-4002, Hungary.
The coupling of matter to the quantized electromagnetic field of a plasmonic or optical cavity can be harnessed to modify and control chemical and physical properties of molecules. In optical cavities, a term known as the dipole self-energy (DSE) appears in the Hamiltonian to ensure gauge invariance. The aim of this work is twofold.
View Article and Find Full Text PDFJ Phys Chem Lett
October 2024
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States.
We simulate the nonadiabatic molecular dynamics of ammonia photodissociation in the presence of an external laser field by using an approximate Floquet Hamiltonian. The dipole-field interaction gives rise to seams of light-induced conical intersection (LICI), which can significantly change the topography of the coupled potential energy surfaces. We perform quasiclassical trajectories based on recently reported diabatic potential energy matrices (DPEM) and dipole matrices.
View Article and Find Full Text PDFJ Chem Theory Comput
March 2024
Departamento de Física, Facultad de Ciencias, Universidad de Chile, Casilla 653, RM 8370449 Santiago, Chile.
We report on a theoretical study of a Cs molecule illuminated by two lasers and show how this can result in novel quantum dynamics. We reveal that these interactions facilitate the bypass of the non-crossing rule, forming light-induced conical intersections and modifiable avoided crossings. Our findings show how laser field orientation and strength, along with initial phase differences, can control molecular-state transitions, especially on the scale.
View Article and Find Full Text PDFPhys Chem Chem Phys
February 2024
Department of Theoretical Physics, Doctoral School of Physics, University of Debrecen, PO Box 400, H-4002 Debrecen, Hungary.
It has been known that electronic conical intersections in a molecular system can also be created by laser light even in diatomics. The direct consequence of these light-induced degeneracies is the appearance of a strong mixing between the electronic and vibrational motions, which has a strong fingerprint on the ultrafast nuclear dynamics. In the present work, pump and probe numerical simulations are performed with the NaH molecule involving the first three singlet electronic states (XΣ(X), AΣ(A) and BΠ(B)) and several light-induced degeneracies in the numerical description.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2023
Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany.
Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [(2-κ P,κ C)Mo(CO) ][OTf] (3 a[OTf]), [(2-κ P,κ C)Fe(CO)][OTf] (3 b[OTf]), and [(2-κ P)Fe(CO) ][OTf] (4[OTf]) were prepared using the triflate salt [(L )P=P(Dipp)][OTf] (2[OTf) as a precursor (L =4,5-dichloro-1,3-bis(2,6-diisiopropylphenyl)-imidazolin-2-yl; Dipp=2,6-diisiopropylphenyl, OTf=triflate).
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