An Accelerated Modular-Orthogonal Ni-Catalyzed Methodology to Symmetric and Nonsymmetric Constitutional Isomeric AB 2 to AB 9 Dendrons Exhibiting Unprecedented Self-Organizing Principles

Percec, Virgil; Wang, Shitao; Huang, Ning; Partridge, Benjamin E.; Wang, Xuefeng; Sahoo, Dipankar; Hoffman, David J.; Malineni, Jagadeesh; Peterca, Mihai; Jezorek, Ryan L.; Zhang, Na; Daud, Hina; Sung, Paul D.; McClure, Emily R.; Song, Se Lin

doi:10.1021/jacs.1c08502

We describe a novel variant of the driven molecular dynamics (DMD) method derived for probing Raman active vibrations. The method is an extension of the conventional alpha-DMD formulation for simulating IR activity by means of coupling an oscillating electric field to the molecule’s dipole moment, miu, and inducing absorption of energy via tuning the field to a resonant frequency. In the present work, we modify the above prescription to invoke Raman activity by coupling two electric fields, i.e., a “Pump” photon of frequency wP and a Stokes photon of frequency wS to the molecule’s polarizability tensor, alpha, with the difference in the frequencies of the two photons w = wP - wS corresponding to the Stokes Raman shift. If a particular w is close to a Raman active vibrational frequency, energy absorption by the molecule ensues. Varying w over the desired frequency range allows identifying and assigning all Raman active vibrational modes, including anharmonic corrections, in the range by means of trajectory analysis. We show that only one element of the full polarizability tensor, and its nuclear derivative, is needed for an alpha-DMD trajectory, making this method well suited for ab initio dynamics implementation. Numerical results using first-principles calculations are presented and discussed for the vibrational fundamentals, combination bands, overtones of H2O, CH4, and the C20 fullerene.

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