The crystal of NLO interest, Barium thiourea chloride (BTC) has been crystallized and is subjected to FT‐IR and NIR FT‐Raman spectral studies along with the quantum chemical computations. The equilibrium geometry, first hyperpolarizability, various bonding features and vibrational wavenumbers have been calculated by B3LYP density functional theory
(DFT) calculations at the LANL2DZ level. The predicted vibrational spectra are in fair agreement with the experiment. The broadening of
stretching wavenumber indicates the intermolecular N‐H…CI hydrogen bonding present in the molecule.