Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 129, Issue 17, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.2996349
Keywords
infrared spectra; organic compounds; ultraviolet spectra; variational techniques; vibronic states; visible spectra
Funding
- Engineering and Physical Sciences Research Council [EP/E005691/1] Funding Source: researchfish
- EPSRC [EP/E005691/1] Funding Source: UKRI
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The Gaussian-based multiconfiguration time-dependent Hartree (G-MCTDH) method is applied to calculate the S(2)(pi pi(*)) absorption spectrum of the pyrazine molecule, whose diffuse structure results from the ultrafast nonadiabatic dynamics at the S(2)-S(1) conical intersection. The 24-mode second-order vibronic-coupling model of Raab [J. Chem. Phys. 110, 936 (1999)] is employed, along with 4-mode and 10-mode reduced-dimensional variants of this model. G-MCTDH can be used either as an all-Gaussian approach or else as a hybrid method using a partitioning into primary modes, treated by conventional MCTDH basis functions, and secondary modes described by Gaussian particles. Comparison with standard MCTDH calculations shows that the method converges to the exact result. The variational, nonclassical evolution of the moving Gaussian basis is a key element in obtaining convergence. For high-dimensional systems, convergence is significantly accelerated if the method is employed as a hybrid scheme.
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