We present molecular dynamics (MD), polarizability driven MD (α-DMD) and pump-probe simulations of Raman spectra of the protonated nitrogen dimer N4H+, and some of its isotopologues, using the CCSD(T)-F12b/aug-cc-pVTZ based potential energy surface in permutationally invariant polynomials (PIP) due to Yu and co-workers [J. Phys. Chem. A 119, 11623, (2015)] and a corresponding PIP-derived CCSD(T)/aug-cc-pVTZ-tr (N: spd, H: sp) polarizability tensor surface (PTS), the latter reported here for the first time. To represent the PTS in terms of a PIP basis, we utilize a recently described formulation for computing the polarizability using a many-body expansion in the orders of dipole-dipole interactions while generating a training set using a novel approach based on a linear regression for potential energy distributions. The MD/α-DMD simulations reveal: (i) a strong Raman activity at 260 cm-1 and 2400 cm-1 corresponding to the symmetric N-N...H bend and symmetric N-N stretch modes, respectively; (ii) a very broad spectral region in 500-2000 cm-1 range assignable to the parallel N...H+...N proton transfer overtone, and (iii) presence of a Fermi-like resonance in the Raman spectrum near 2400 cm-1 between the 1Σg+ N-N stretch fundamental and the Πu overtone corresponding to perpendicular N...H+...N proton transfer.
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